Halogenated activated carbon compositions and methods of making and using same

ABSTRACT

This disclosure provides a halogenated activated carbon composition comprising carbon, a halogenated compound and a salt. In some embodiments, the halogenated compound and the salt comprise a naturally occurring salt mixture, as may be obtained from ocean water, salt lake water, rock salt, salt brine wells, for example. In some embodiments, the naturally occurring salt mixture comprises Dead Sea salt.

PRIORITY DATA

This application is a continuation of U.S. patent application Ser. No.14/922,829 filed on Oct. 26, 2015, which claims priority to U.S.Provisional Patent Application Ser. No. 62/068,258, filed Oct. 24, 2014,the entire contents of which are incorporated herein by reference andrelied upon.

FIELD

The present disclosure generally relates to halogenated biogenicactivated carbon compositions and methods.

BACKGROUND

Activated carbon was first produced commercially at the beginning of the20th century and was used initially to decolorize sugar, then later toremove taste and odor from water. Granular activated carbon was firstdeveloped for gas masks and has been used subsequently for a variety ofadditional purposes such as solvent recovery and air purification.Processes to produce activated carbon generally require large energyinputs and suffer from low yields. Most processes require two distinctsteps: pyrolysis of the carbonaceous raw material followed by activationof the pyrolyzed solids. Pyrolysis typically involves directly heatingthe carbonaceous substrate in a low-oxygen environment. Activationgenerally involves application of steam or carbon dioxide to increasesurface area of the pyrolyzed solids.

Mercury emissions from coal-fired power plants are the subject ofgovernmental regulation. The control of mercury emissions is complicatedby the several forms mercury may take within combustion flue gases. Forexample, at combustion temperatures, mercury is present in flue gases inits elemental form, Hg⁰, which may be difficult to control because it iseasily volatized and is unreactive. Mercury reacts with carbon as fluegases cool below 550° C., and such reactions may convert mercury to itshighly reactive, oxidized form, Hg²⁺. Mercury may also be absorbed infly ash and/or other flue gas particles to form particulate-boundmercury.

Despite its promise, the cost of using activated carbon for mercurycontrol has been high. A more efficient activated carbon composition isneeded for controlling mercury and other emissions in an economic way.Improved processes to produce these activated carbon products are alsocurrently needed.

SUMMARY

In some embodiments, the disclosure provides a halogenated activatedcarbon composition, the composition comprising, on a dry basis, at least85 wt % carbon; a halogenated compound; and a salt, wherein thehalogenated compound and the salt are present in a total amount of about0.1 wt % to about 15 wt %. In some embodiments, the halogenated compoundand/or the salt comprises at least two halogens or salts thereof. Insome embodiments, at least a portion of the carbon comprises biogeniccarbon (e.g., carbon derived from a feedstock comprising biomass).

In some embodiments, the halogenated compound may be a salt, such as ametal halide. In other embodiments, the halogenated compound may be amolecular halogen (e.g., molecular bromine, Br₂) or a halocarbon (e.g.,chloroform, CHCl₃).

In some embodiments, the halogenated activated carbon compositioncomprises at least 90 wt % carbon or at least 95 wt % carbon. In someembodiments, the halogenated compound and the salt are present in atotal amount of about 1 wt % to about 10 wt %.

In some embodiments, the halogenated activated carbon comprises two ormore salts selected from the group consisting of magnesium chloride,potassium chloride, sodium chloride, and calcium chloride.

The halogenated compound and/or the salt includes at least one anionselected from the group consisting of chloride, bromide, iodide,fluoride, sulfate, nitrate, and phosphate. In some embodiments, thehalogenated compound and/or the salt comprises at least two anionsselected from the group consisting of chloride, bromide, iodide,fluoride, sulfate, nitrate, and phosphate. For example, the halogenatedcompound and/or the salt may include ferric chloride sulfate, FeClSO₄.

In some embodiments, the halogenated compound and/or the salt alsoincludes at least one cation selected from the group consisting ofmagnesium, potassium, calcium, sodium, ammonium, copper, cobalt, nickel,manganese, iron, zinc, molybdenum, and tungsten. In some embodiments,the halogen compound and/or the salt comprises at least two cationsselected from the group consisting of magnesium, potassium, calcium,sodium, ammonium, copper, cobalt, nickel, manganese, iron, zinc,molybdenum, and tungsten.

In some preferred embodiments, the halogenated compound and/or the saltcomprises a naturally occurring salt mixture, or is derived from anaturally occurring salt mixture. A naturally occurring salt mixture maybe obtained from ocean water, salt lake water, rock salt, salt brinewells, or combinations thereof, for example. Naturally occurring saltmixtures typically contain various minerals, in addition to salts.

In some embodiments, the naturally occurring salt mixture comprises,consists essentially of, or consists of Dead Sea salt. In certainembodiments, the naturally occurring salt mixture comprises, consistsessentially of, or consists of Dead Sea salt and Great Salt Lake salt,or Dead Sea salt and sea salt derived from ocean water.

In some embodiments, the halogenated compound and/or the salt includesabout 10 wt % to about 90 wt % magnesium chloride, such as about 25 wt %to about 40 wt % magnesium chloride. In some embodiments, thehalogenated compound and/or the salt includes about 5 wt % to about 75wt % potassium chloride, such as about 15 wt % to about 35 wt %potassium chloride. In these or other embodiments, the halogenatedcompound and/or the salt includes about 1 wt % to about 25 wt % sodiumchloride, such as about 2 wt % to about 10 wt % sodium chloride.

In some embodiments, the halogenated compound and/or the salt includesmagnesium chloride (MgCl₂), potassium chloride (KCl), and sodiumchloride (NaCl), wherein the weight ratio of (MgCl₂+KCl)/NaCl is atleast about 5 or at least about 10.

In some embodiments, the halogenated compound and/or the salt includesfrom about 0.1 wt % to about 5 wt % bromide ions, such as about 0.2 wt %to about 2 wt % bromide ions. In some embodiments, the halogenatedcompound and/or the salt includes about 0.01 wt % to about 1 wt %sulfate ions, such as about 0.01 wt % to about 0.5 wt % sulfate ions.

Other embodiments provide a biogenic activated carbon compositioncomprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen; and

about 0.1 wt % to about 10 wt % of at least one anion selected from thegroup consisting of chloride, bromide, iodide, fluoride, sulfate,nitrate, phosphate, and combinations thereof.

In some embodiments, the composition comprises, on a dry basis, about0.5 wt % to about 10 wt % of the at least one anion, such as about 2 wt% to about 8 wt % of the at least one anion.

Other embodiments provide a biogenic activated carbon compositioncomprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen; and

about 0.1 wt % to about 10 wt % of at least one cation selected from thegroup consisting of magnesium, potassium, calcium, sodium, ammonium,copper, cobalt, nickel, manganese, iron, zinc, molybdenum, tungsten, andcombinations thereof.

In some embodiments, the composition comprises, on a dry basis, about0.5 wt % to about 10 wt % of the at least one cation, such as about 2 wt% to about 8 wt % of the at least one cation.

Other embodiments provide a biogenic activated carbon compositioncomprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen; and

a halogenated compound comprising a salt selected from the groupconsisting of magnesium chloride, potassium chloride, sodium chloride,calcium chloride, and combinations thereof; and a salt, wherein thehalogenated compound and the salt are present in a total amount of about0.2 wt % to about 20 wt %.

In some embodiments, the halogenated compound and the salt are presentin a total amount, on a dry basis, of about 1 wt % to about 15 wt %,such as about 2 wt % to about 10 wt %.

In some embodiments, the halogenated compound and/or the salt includesabout 10 wt % to about 90 wt % magnesium chloride, such as from about 25wt % to about 40 wt % magnesium chloride. In some embodiments, thehalogenated compound includes about 5 wt % to about 75 wt % potassiumchloride, such as about 15 wt % to about 35 wt % potassium chloride. Insome embodiments, the halogenated compound and/or the salt includesabout 1 wt % to about 25 wt % sodium chloride, such as about 2 wt % toabout 10 wt % sodium chloride. In some embodiments, the halogenatedcompound and/or the salt includes magnesium chloride (MgCl₂), potassiumchloride (KCl), and sodium chloride (NaCl), and wherein the weight ratioof (MgCl₂+KCl)/NaCl is at about least 5, at least about 6, at leastabout 7, at least about 8, at least about 9, or at least 10.

In some embodiments, the halogenated compound and/or the salt includesabout 0.1 wt % to about 5 wt % bromide ions, such as about 0.2 wt % toabout 2 wt % bromide ions, in some embodiments. In some embodiments, thehalogenated compound and/or the salt includes about 0.01 wt % to about 1wt % sulfate ions, such as about 0.01 wt % to about 0.5 wt % sulfateions.

In some embodiments, the halogenated compound and/or the salt maycomprise, consist essentially of, or consist of a naturally occurringsalt mixture, such as (but not limited to) a salt mixture or aderivative thereof obtained from ocean water, salt lake water, rocksalt, salt brine wells, or combinations thereof. In some embodiments,the naturally occurring salt mixture comprises, consists essentially of,or consists of Dead Sea salt. In other embodiments, the naturallyoccurring salt mixture comprises, consists essentially of, or consistsof Dead Sea salt and Great Salt Lake salt or Dead Sea salt and sea saltderived from ocean water.

The present disclosure provides an activated carbon product comprisingactivated carbon (which may comprise, consist essentially of, or consistof biogenic activated carbon) and Dead Sea salt. The present disclosurealso provides an activated carbon product consisting essentially ofactivated carbon (which may comprise, consist essentially of, or consistof biogenic activated carbon) and Dead Sea salt. In some embodiments, anactivated carbon product comprises, consists essentially of, or consistsof activated carbon, Dead Sea salt, and Great Salt Lake salt.

In some embodiments, the disclosure provides a process for producing ahalogenated activated carbon composition, the process comprising:

(a) providing a starting carbon-containing feedstock;

(b) converting the feedstock to an activated carbon intermediate;

(c) combining the activated carbon intermediate, during step (b) orfollowing step (b), with at least two halogens or salts thereof, to forma mixture; and

(d) recovering a halogenated activated carbon composition from themixture,

wherein the halogenated activated carbon composition comprises, on a drybasis, at least 85 wt % carbon and about 0.1 wt % to about 15 wt % ofthe at least two halogens or salts thereof.

The at least two halogens or salts thereof may be introduced in solidform, dissolved or suspended in liquid solution, in a vapor or mist, orany combinations of the foregoing. In some embodiments, the at least twohalogens or salts thereof are introduced as an aqueous solution,followed by evaporating water to generate a dried form of the mixture.

During step (c), in some embodiments, a chemical reaction or physicalreaction may occur between the activated carbon intermediate and one ormore of the at least two halogens or salts thereof.

In some embodiments, the process of step (b) further comprises thesubsteps of:

(i) in one or more indirectly heated reaction zones, mechanicallycountercurrently contacting the feedstock with a vapor stream comprisinga substantially inert gas and an activation agent comprising at leastone of water or carbon dioxide, to generate solids, condensable vapors,and non-condensable gases, wherein the condensable vapors and thenon-condensable gases enter the vapor stream;

(ii) removing at least a portion of the vapor stream from the reactionzone(s), to generate a separated vapor stream;

(iii) recycling at least a portion of the separated vapor stream, or athermally treated form thereof, to substep (i); and

(iv) recovering at least a portion of the solids from the reactionzone(s) as the activated carbon intermediate.

During substep (iii), at least a portion of the separated vapor streammay be thermally oxidized, generating oxidation heat that is thenutilized, at least in part, to dry the activated carbon intermediate.

Some embodiments provide a process for producing a halogenated activatedcarbon composition, the process comprising:

(a) providing a starting carbon-containing feedstock;

(b) combining the feedstock with at least two halogens or salts thereof;

(c) converting the feedstock, combined with the at least two halogens orsalts thereof, to a halogenated activated carbon composition; and

(d) recovering the halogenated activated carbon composition,

wherein the halogenated activated carbon composition comprises, on a drybasis, at least 85 wt % carbon and about 0.1 wt % to about 15 wt % ofthe at least two halogens or salts thereof.

The at least two halogens and/or salts thereof may be introduced insolid form, dissolved or suspended in liquid solution, in a vapor ormist, or any combinations of the foregoing. In some embodiments, duringstep (c), a chemical reaction or physical reaction occurs between thefeedstock and one or more of the at least two halogens or salts thereof.

In some embodiments, the process of step (c) may further include thesubsteps of:

(i) in one or more indirectly heated reaction zones, mechanicallycountercurrently contacting the feedstock with a vapor stream comprisinga substantially inert gas and an activation agent comprising at leastone of water or carbon dioxide, to generate solids, condensable vapors,and non-condensable gases, wherein the condensable vapors and thenon-condensable gases enter the vapor stream;

(ii) removing at least a portion of the vapor stream from the reactionzone(s), to generate a separated vapor stream;

(iii) recycling at least a portion of the separated vapor stream, or athermally treated form thereof, to substep (i); and

(iv) recovering at least a portion of the solids from the reactionzone(s) as the halogenated activated carbon composition.

During substep (iii), at least a portion of the separated vapor streammay be thermally oxidized, generating oxidation heat that is thenutilized, at least in part, dry the halogenated activated carboncomposition.

Any of these processes may be a continuous, semi-continuous, or batch.

The carbon-containing feedstock preferably includes biomass, such asbiomass is selected from the group consisting of softwood chips,hardwood chips, timber harvesting residues, tree branches, tree stumps,leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, ricestraw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugarbeets, sugar beet pulp, sunflowers, sorghum, canola, algae, miscanthus,alfalfa, switchgrass, fruits, fruit shells, fruit stalks, fruit peels,fruit pits, vegetables, vegetable shells, vegetable stalks, vegetablepeels, vegetable pits, grape pumice, almond shells, pecan shells,coconut shells, coffee grounds, food waste, commercial waste, grasspellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paperpackaging, paper trimmings, food packaging, lignin, animal manure,municipal solid waste, municipal sewage, and combinations thereof.

In some embodiments, the halogen compound(s) utilized in these processescomprises, consists essentially of, or consists of a naturally occurringsalt mixture, such as (but not limited to) naturally occurring saltmixtures derived from a source selected from the group consisting ofocean water, salt lake water, rock salt, salt brine wells, andcombinations thereof. In these or other embodiments, the halogencompound(s) comprises a recycled salt obtained after use of thehalogenated activated carbon composition (such as following combustionof the activated carbon). In other embodiments, the halogen compound(s)may be obtained from a mixture of halogenated species, such as crudehalogen mixtures obtained from industrial processes (e.g.,salt-containing wastes or byproducts). In some embodiments, a process ofproducing a halogenated activated carbon composition comprises addingthe halogens or salts thereof as a mixture of halogenated species. Inother embodiments, a process of producing a halogenated activated carboncomposition comprises adding the halogens or salts thereof as pure orsubstantially pure halogen species or salts thereof.

The present disclosure provides activated carbon products produced byany of the disclosed processes, and apparatus configured to carry outany of the disclosed processes. The present disclosure also providesmethods of using the activated carbon compositions or products for oneor more applications selected from the group consisting of emissionscontrol, mercury removal, water purification, groundwater treatment,wastewater treatment, removal of odor-producing or taste-producingcompounds from a liquid, energy storage, energy transfer, capacitance,ion storage, and ion transfer.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a representative view of a test bed holder apparatusconfigured according to one embodiment of the present disclosure.

FIG. 2 is a schematic representation of a mercury vapor adsorptionanalysis system configured according to one embodiment of the presentdisclosure.

FIG. 3 is a plot of mercury breakthrough over time for varioushalogenated activated carbon compositions consistent with the presentdisclosure.

DETAILED DESCRIPTION

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contextclearly indicates otherwise. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this disclosurebelongs.

Unless otherwise indicated, all numbers expressing reaction conditions,stoichiometries, concentrations of components, and so forth used in thespecification and claims are to be understood as being modified in allinstances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the followingspecification and attached claims are approximations that may varydepending at least upon a specific analytical technique.

The term “comprising,” which is synonymous with “including,”“containing,” or “characterized by” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. “Comprising”is a term of art used in claim language which means that the named claimelements are essential, but other claim elements may be added and stillform a construct within the scope of the claim.

As used herein, the phase “consisting of” excludes any element, step, oringredient not specified in the claim. When the phrase “consists of” (orvariations thereof) appears in a clause of the body of a claim, ratherthan immediately following the preamble, it limits only the element setforth in that clause; other elements are not excluded from the claim asa whole. As used herein, the phase “consisting essentially of” limitsthe scope of a claim to the specified elements or method steps, plusthose that do not materially affect the basis and novelcharacteristic(s) of the claimed subject matter.

With respect to the terms “comprising,” “consisting of” and “consistingessentially of” where one of these three terms is used herein, thepresently disclosed and claimed subject matter may include the use ofeither of the other two terms. Thus in some embodiments not otherwiseexplicitly recited, any instance of “comprising” may be replaced by“consisting of” or, alternatively, by “consisting essentially of”

“Pyrolysis” and “pyrolyze” generally refer to thermal decomposition of acarbonaceous material. In pyrolysis, less oxygen is present than isrequired for complete combustion of the material, such as less than 10%,less than 5%, less than 1%, less than 0.5%, less than 0.1%, or less than0.01% of the oxygen that is required for complete combustion. In someembodiments, pyrolysis is performed in the absence of oxygen.

For present purposes, “biogenic” is intended to mean a material (whethera feedstock, product, or intermediate) that includes an element, such ascarbon, that is renewable on time scales of months, years, or decades.Non-biogenic materials may be non-renewable, or may be renewable on timescales of centuries, thousands of years, millions of years, or evenlonger geologic time scales. Note that a biogenic material may include amixture of biogenic and non-biogenic sources.

For present purposes, “reagent” is intended to mean a material in itsbroadest sense; a reagent may be a fuel, a chemical, a material, acompound, an additive, a blend component, a solvent, and so on. Areagent is not necessarily a chemical reagent that causes orparticipates in a chemical reaction. A reagent may or may not be achemical reactant; it may or may not be consumed in a reaction. Areagent may be a chemical catalyst for a particular reaction. A reagentmay cause or participate in adjusting a mechanical, physical, orhydrodynamic property of a material to which the reagent may be added.For example, a reagent may be introduced to a metal to impart certainstrength properties to the metal. A reagent may be a substance ofsufficient purity (which, in the current context, is typically carbonpurity) for use in chemical analysis or physical testing.

The biogenic activated carbon will have relatively high carbon contentas compared to the initial feedstock utilized to produce the biogenicactivated carbon. A biogenic activated carbon as provided herein willnormally contain greater than about half its weight as carbon, since thetypical carbon content of biomass is no greater than about 50 wt %. Moretypically, but depending on feedstock composition, a biogenic activatedcarbon will contain at least 55 wt %, at least 60 wt %, at least 65 wt%, at least 70 wt %, at least 75 wt %, at least 80 wt % 85 wt %, or atleast 90 wt % carbon.

Notwithstanding the foregoing, the term “biogenic activated carbon” isused herein for practical purposes to consistently describe materialsthat may be produced by processes and systems of the disclosure, invarious embodiments. Limitations as to carbon content, or any otherconcentrations, shall not be imputed from the term itself but ratheronly by reference to particular embodiments and equivalents thereof. Forexample it will be appreciated that a starting material having very lowinitial carbon content, subjected to the disclosed processes, mayproduce a biogenic activated carbon that is highly enriched in carbonrelative to the starting material (high yield of carbon), butnevertheless relatively low in carbon (low purity of carbon), includingless than 50 wt % carbon.

As used herein, the term “halogenated compound” refers to a halogenallotrope, a compound, a salt or a mineral that includes at least onehalogen anion (e.g., fluoride, chloride, bromide, iodide, or acombination thereof), or a mixture of more than one such compound, saltor mineral.

As used herein, the term “salt” refers to an ionic compound and/or amineral including a mixture of cations and anions, or a mixture of morethan one such ionic compound and/or minerals. In some embodiments, thesalt includes an ionic compound and/or a mineral that includes at leastone halogen anion.

Some embodiments are premised on the surprising discovery thatincorporating halogen compounds and/or salts into activated carbonproduces a halogenated activated carbon composition that is particularlyeffective for mercury control and other applications. Some embodimentsutilize crude sources of halogen compounds and/or salts, such asnaturally occurring salt mixtures, rather than purified salts or otheradditives.

In some embodiments, the disclosure provides a halogenated activatedcarbon composition, the composition comprising, on a dry basis, at least75 wt %, 80 wt %, 85 wt %, or 90 wt % carbon, a halogenated compound,and a salt, wherein the halogenated compound and the salt are present ina total amount of about 0.1 wt % to about 20 wt %.

In some embodiments, the halogenated activated carbon compositioncomprises at least 90 wt % carbon or at least 95 wt % carbon. Some orall of the carbon is preferably (but not necessarily) biogenic carbonderived from biomass.

In some embodiments, the halogenated compound and the salt are presentin a total amount of about 0.5 wt % to about 15 wt %, or about 1 wt % toabout 15 wt %. In various embodiments, the halogenated compound and thesalt are present in a total amount of about 0.5 wt %, about 1 wt %,about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %,about 12 wt %, about 13 wt %, about 14 wt %, or about 15 wt %.

In some embodiments, the halogenated compound and/or the salt comprise(e.g., collectively comprise) two or more species selected from thegroup consisting of magnesium chloride, potassium chloride, sodiumchloride, and calcium chloride.

Collectively, the halogenated compound and the salt comprises at leastone anion selected from the group consisting of chloride, bromide,iodide, fluoride, sulfate, nitrate, and phosphate. In some embodiments,the halogenated compound and the salt comprise at least two anionsselected from the group consisting of chloride, bromide, iodide,fluoride, sulfate, nitrate, and phosphate. For example, in someembodiments the halogenated compound and/or the salt may include ferricchloride sulfate, FeClSO₄.

Collectively, the halogenated compound and the salt comprise at leastone cation selected from the group consisting of magnesium, potassium,calcium, sodium, ammonium, copper, cobalt, nickel, manganese, iron,zinc, molybdenum, and tungsten. In some embodiments, the halogencompound and the salt comprise at least two cations selected from thegroup consisting of magnesium, potassium, calcium, sodium, ammonium,copper, cobalt, nickel, manganese, iron, zinc, molybdenum, and tungsten.

In some embodiments, the halogen compound and the salt comprise, consistessentially of, or consist of a naturally occurring salt mixture, or isderived from a naturally occurring salt mixture. A naturally occurringsalt mixture may be obtained from ocean water, salt lake water, rocksalt, salt brine wells, or combinations thereof, for example. Naturallyoccurring salt mixtures typically contain various minerals, in additionto salts. The present inventors have found that, unexpectedly, inclusionof naturally occurring salt mixtures improves the performance andstability of the activated carbon, especially after the activated carbonhas been used, for example, to adsorb a contaminant (e.g., Hg).

In some embodiments, the naturally occurring salt mixture comprises,consists essentially of, or consists of Dead Sea salt (e.g., salt thatis obtained from the Dead Sea in the Jordan Rift Valley). The exactcomposition of the Dead Sea water varies mainly with season, depth, andtemperature, but predominantly includes magnesium chloride, potassiumchloride, and high amounts of bromide salts. Because the saltconcentration is so high (typically more than 30 wt %, compared to onlyabout 3.5% in sea water), Dead Sea water may be utilized withoutsubstantial refinement as the source of the halogenated compound and/orthe salt in activated carbon compositions and processes disclosedherein. In other embodiments, the salts will first be concentrated byevaporation or other means for separating water from the salts.

In some embodiments, the naturally occurring salt mixture comprises,consists essentially of, or consists of Great Salt Lake (e.g., salt thatis obtained from the Great Salt Lake in Utah). The Great Salt Lake isthe largest salt water lake in the Western Hemisphere. It has very highsalinity (about 5 wt % to 27 wt %), far saltier than sea water, and itsmineral content is constantly increasing. The ionic composition issimilar to seawater, much more so than the Dead Sea's water. Compared tothe ocean, Great Salt Lake water is slightly enriched in potassium anddepleted in calcium. Because the salt concentration is so high, GreatSalt Lake water may be utilized directly without substantial refinementas the source of the halogenated compound and/or the salt in activatedcarbon compositions and processes disclosed herein. In otherembodiments, the salts will first be concentrated by evaporation orother means for separating water from the salts.

In some embodiments, the halogenated compound and/or the salt comprises,consists essentially of, or consists of a mixture obtained from anotherendorheic water body, such as the Aral Sea, the Caspian Sea, Lake Vandain Antarctica, Lake Assal (Djibouti, Africa), and/or a hypersaline pondand/or lake of the McMurdo Dry Valleys in Antarctica.

In certain embodiments, the naturally occurring salt mixture comprises,consists essentially of, or consists of Dead Sea salt and Great SaltLake salt. In certain embodiments, the naturally occurring salt mixturecomprises, consists essentially of, or consists of Dead Sea salt and seasalt derived from ocean water. In certain embodiments, the naturallyoccurring salt mixture comprises, consists essentially of, or consistsof Great Salt Lake salt and sea salt derived from ocean water.

Other naturally occurring salt mixtures are obtained from undergroundformations (e.g., rock salt) or salt brine wells that are underground.Such sources of naturally occurring salt mixtures may be used directly,or combined with one or more other sources such as those describedabove.

In some embodiments, the halogenated compound and/or the salt includesabout 10 wt % to about 90 wt % magnesium chloride, such as about 25 wt %to about 40 wt % magnesium chloride. In some embodiments, thehalogenated compound and/or the salt includes about 5 wt % to about 75wt % potassium chloride, such as about 15 wt % to about 35 wt %potassium chloride. In these or other embodiments, the halogenatedcompound and/or the salt includes about 1 wt % to about 25 wt % sodiumchloride, such as about 2 wt % to about 10 wt % sodium chloride.

In some embodiments, the halogenated compound and/or the salt includeseach of magnesium chloride (MgCl₂), potassium chloride (KCl), and sodiumchloride (NaCl), in some embodiments, wherein the weight ratio of(MgCl₂+KCl)/NaCl is at least about 2, at least about 3, at least about4, at least about 5, at least about 6, at least about 7, at least about8, at least about 9, at least about 10, at least about 11, at leastabout 12, at least about 13, at least about 14, or at least about 15.

In some embodiments, the halogenated compound and/or the salt includesabout 0.1 wt % to about 5 wt % bromide ions (Br), such as about 0.2 wt %to about 2 wt % bromide ions. The halogenated compound and/or the saltmay include, for example, about 0.2 wt %, about 0.4 wt %, about 0.7 wt%, about 1 wt %, about 1.2 wt %, about 1.5 wt %, about 1.8 wt %, or morethan about 1.8 wt % bromide ions.

In some embodiments, the halogenated compound and/or the salt includesabout 0.01 wt % to about 1 wt % sulfate ions (SO₄ ²⁻), such as about0.01 wt % to about 0.5 wt % sulfate ions. The halogenated compoundand/or the salt may include, for example, about 0.02 wt %, about 0.05 wt%, about 0.1 wt %, about 0.15 wt %, about 0.2 wt %, or about 0.3 wt %sulfate ions.

In some embodiments, the present disclosure provides a biogenicactivated carbon composition comprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen; and

about 0.1 wt % to about 10 wt % of at least one anion selected from thegroup consisting of chloride, bromide, iodide, fluoride, sulfate,nitrate, phosphate, and combinations thereof.

In some embodiments, the composition comprises, on a dry basis, about0.5 wt % to about 10 wt % of the at least one anion, such as about 2 wt% to about 8 wt % of the at least one anion, or about 1 wt %, about 2 wt%, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, or about 10 wt % of the anion.

In some embodiments, the present disclosure provides a biogenicactivated carbon composition comprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen; and

about 0.1 wt % to about 10 wt % of at least one cation selected from thegroup consisting of magnesium, potassium, calcium, sodium, ammonium,copper, cobalt, nickel, manganese, iron, zinc, molybdenum, tungsten, andcombinations thereof.

In some embodiments, the composition comprises, on a dry basis, about0.5 wt % to about 10 wt % of the at least one cation, such as about 2 wt% to about 8 wt % of the cation or cation mixture, or about 1 wt %,about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, or about 10 wt % of the cationor cation mixture.

In some embodiments, the present disclosure provides a biogenicactivated carbon composition comprising, on a dry basis:

80 wt % or more total carbon;

10 wt % or less hydrogen;

a halogenated compound comprising a salt selected from the groupconsisting of magnesium chloride, potassium chloride, sodium chloride,calcium chloride, and combinations thereof; and

a salt,

wherein the halogenated compound and the salt are present in a totalamount of about 0.2 wt % to about 20 wt %.

In some embodiments, the halogenated compound and the salt are presentin a total amount, on a dry basis, of about 1 wt % to about 15 wt %,such as about 2 wt % to about 10 wt %, or about 1 wt %, about 2 wt %,about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %,about 13 wt %, about 14 wt %, or about 15 wt %.

The halogenated compound and/or the salt includes, in some embodiments,about 10 wt % to about 90 wt % magnesium chloride, such as about 25 wt %to about 40 wt % magnesium chloride. The halogenated compound and/or thesalt includes, in some embodiments, about 5 wt % to about 75 wt %potassium chloride, such as about 15 wt % to about 35 wt % potassiumchloride. The halogenated compound and/or the salt includes, in someembodiments, about 1 wt % to about 25 wt % sodium chloride, such asabout 2 wt % to about 10 wt % sodium chloride. In some embodiments, thehalogen compound includes magnesium chloride (MgCl₂), potassium chloride(KCl), and sodium chloride (NaCl), and wherein the weight ratio of(MgCl₂+KCl)/NaCl is at least 2, at least 3, at least 4, at least 5, atleast 6, at least 7, at least 8, at least 9, or at least 10.

In some embodiments, the halogenated compound and/or the salt includesabout 0.1 wt % to about 5 wt % bromide ions, such as about 0.2 wt % toabout 2 wt % bromide ions. In some embodiments, the halogenated compoundand/or the salt includes about 0.01 wt % to about 1 wt % sulfate ions,such as about 0.01 wt % to about 0.5 wt % sulfate ions.

The halogenated compound and/or the salt may comprise, consistessentially of, or consist of a naturally occurring salt mixture, suchas (but not limited to) a salt mixture or a derivative thereof obtainedfrom ocean water, salt lake water, rock salt, salt brine wells, orcombinations thereof. In some embodiments, the naturally occurring saltmixture comprises, consists essentially of, or consists of Dead Seasalt. In other embodiments, the naturally occurring salt mixturecomprises, consists essentially of, or consists of Dead Sea salt andGreat Salt Lake salt or Dead Sea salt and sea salt derived from oceanwater.

The present disclosure provides an activated carbon product comprisingactivated carbon (which may comprise, consist essentially of, or consistof biogenic activated carbon) and Dead Sea salt. The present disclosurealso provides an activated carbon product consisting essentially ofactivated carbon (which may comprise, consist essentially of, or consistof biogenic activated carbon) and Dead Sea salt. In some embodiments, anactivated carbon product comprises, consists essentially of, or consistsof activated carbon, Dead Sea salt, and Great Salt Lake salt.

In some embodiments, the present disclosure provides a process forproducing a halogenated activated carbon composition, the processcomprising:

(a) providing a carbon-containing feedstock;

(b) converting the feedstock to an activated carbon intermediate;

(c) combining the activated carbon intermediate, during step (b) orfollowing step (b), with at least two halogens or salts thereof, to forma mixture; and

(d) recovering a halogenated activated carbon composition from themixture,

wherein the halogenated activated carbon composition comprises, on a drybasis, at least 85 wt % carbon and about 0.1 wt % to about 15 wt % ofthe at least two halogens or salts thereof.

The at least two halogens or salts thereof may be introduced at anypoint in the process. The at least two halogens or salts thereof may beintroduced in solid form, dissolved or suspended in liquid solution, ina vapor or mist, or any combinations of the foregoing. In someembodiments, the at least two halogens or salts thereof are introducedas an aqueous solution, followed by evaporating water to generate adried form of the mixture.

During step (c), a chemical reaction or physical reaction may occurbetween the activated carbon intermediate and one or more of the atleast two halogens or salts thereof. For example, metal carbides mayform between metal cations and carbon, or anions may react with hydrogenpresent in the activated carbon. Salts, cations, or anions may also bephysically adsorbed, absorbed, or intercalated within the carbon.

In some embodiments, the process of step (b) comprises the substeps of:

(i) in one or more indirectly heated reaction zones, mechanicallycountercurrently contacting the feedstock with a vapor stream comprisinga substantially inert gas and an activation agent comprising at leastone of water or carbon dioxide, to generate solids, condensable vapors,and non-condensable gases, wherein the condensable vapors and thenon-condensable gases enter the vapor stream;

(ii) removing at least a portion of the vapor stream from the reactionzone(s), to generate a separated vapor stream;

(iii) recycling at least a portion of the separated vapor stream, or athermally treated form thereof, to substep (i); and

(iv) recovering at least a portion of the solids from the reactionzone(s) as the activated carbon intermediate.

During substep (iii), at least a portion of the separated vapor streammay be thermally oxidized, generating oxidation heat that is thenutilized, at least in part, to dry the activated carbon intermediate.

Some embodiments of the present disclosure provide a process forproducing a halogenated activated carbon composition, the processcomprising:

(a) providing a carbon-containing feedstock;

(b) combining the feedstock with a at least two halogens or saltsthereof;

(c) converting the feedstock, combined with the at least two halogens orsalts thereof, to a halogenated activated carbon composition; and

(d) recovering the halogenated activated carbon composition,

wherein the halogenated activated carbon composition comprises, on a drybasis, at least 85 wt % carbon and about 0.1 wt % to about 15 wt % ofthe at least two halogens or salts thereof.

The at least two halogens or salts thereof may be introduced in solidform, dissolved or suspended in liquid solution, in a vapor or mist, orany combinations of the foregoing, at one or more points in the process.In some embodiments, during step (c), a chemical reaction or physicalreaction occurs between the feedstock and one or more of the at leasttwo halogens or salts thereof.

In some embodiments, the process of step (c) may further include thesubsteps of:

(i) in one or more indirectly heated reaction zones, mechanicallycountercurrently contacting the feedstock with a vapor stream comprisinga substantially inert gas and an activation agent comprising at leastone of water or carbon dioxide, to generate solids, condensable vapors,and non-condensable gases, wherein the condensable vapors and thenon-condensable gases enter the vapor stream;

(ii) removing at least a portion of the vapor stream from the reactionzone(s), to generate a separated vapor stream;

(iii) recycling at least a portion of the separated vapor stream, or athermally treated form thereof, to substep (i); and

(iv) recovering at least a portion of the solids from the reactionzone(s) as the halogenated activated carbon composition.

During substep (iii), at least a portion of the separated vapor streammay be thermally oxidized, generating oxidation heat that is thenutilized, at least in part, dry the halogenated activated carboncomposition.

Any of these processes may be a continuous, semi-continuous, or batch.

The carbon-containing feedstock preferably includes biomass, such asbiomass is selected from the group consisting of softwood chips,hardwood chips, timber harvesting residues, tree branches, tree stumps,leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, ricestraw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugarbeets, sugar beet pulp, sunflowers, sorghum, canola, algae, miscanthus,alfalfa, switchgrass, fruits, fruit shells, fruit stalks, fruit peels,fruit pits, vegetables, vegetable shells, vegetable stalks, vegetablepeels, vegetable pits, grape pumice, almond shells, pecan shells,coconut shells, coffee grounds, food waste, commercial waste, grasspellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paperpackaging, paper trimmings, food packaging, lignin, animal manure,municipal solid waste, municipal sewage, and combinations thereof.

In some embodiments, the feedstock comprises biomass, coal, or a mixtureof biomass and coal. “Biomass,” for purposes of this disclosure, shallbe construed as any biogenic feedstock or mixture of a biogenic andnon-biogenic feedstock. Elementally, biomass includes at least carbon,hydrogen, and oxygen. The methods and apparatus of the disclosure canaccommodate a wide range of feedstocks of various types, sizes, andmoisture contents.

Various embodiments of the present disclosure are also useful forcarbon-containing feedstocks other than biomass, such as a fossil fuel(e.g., coal or petroleum coke), or any mixtures of biomass and fossilfuels (such as biomass/coal mixtures). In some embodiments, a biogenicfeedstock is, or includes, coal, oil shale, crude oil, asphalt, orsolids from crude-oil processing (such as petcoke). Feedstocks mayinclude waste tires, recycled plastics, recycled paper, and other wasteor recycled materials. Any method, apparatus, or system described hereinmay be used with any carbonaceous feedstock. Carbon-containingfeedstocks may be transportable by any known means, such as by truck,train, ship, barge, tractor trailer, or any other vehicle or means ofconveyance.

Typically, regardless of the feedstocks chosen, there can be (in someembodiments) screening to remove undesirable materials. The feedstockmay optionally be dried prior to processing. The feedstock may be a wetfeedstock.

The feedstock employed may be provided or processed into a wide varietyof particle sizes or shapes. For example, the feed material may be afine powder, or a mixture of fine and coarse particles. The feedmaterial may be in the form of large pieces of material, such as woodchips or other forms of wood (e.g., round, cylindrical, square, etc.).In some embodiments, the feed material comprises pellets or otheragglomerated forms of particles that have been pressed together orotherwise bound, such as with a binder.

In some embodiments, the halogenated compounds and/or the salts of thehalogenated activated carbon compositions and processes disclosed hereincomprise, consist essentially of, or consist of a naturally occurringsalt mixture, such as (but not limited to) naturally occurring saltmixtures derived from a source selected from the group consisting ofocean water, salt lake water, rock salt, salt brine wells, andcombinations thereof.

In these or other embodiments, the halogenated compound and/or the saltmay include a recycled salt obtained after use of the halogenatedactivated carbon composition (such as following combustion of spentactivated carbon). Other sources of halogenated compounds and/or saltsmay be used, such as crude halogenated compounds or compositionsobtained from industrial processes (e.g., salt-containing wastes orbyproducts).

The present disclosure provides activated carbon products produced byany of the disclosed processes, and apparatus configured to carry outany of the disclosed processes. The present disclosure also providesmethods of using the activated carbon compositions or products for oneor more applications selected from the group consisting of emissionscontrol, mercury removal, water purification, groundwater treatment,wastewater treatment, removal of odor-producing or taste-producingcompounds from a liquid, energy storage, energy transfer, capacitance,ion storage, and ion transfer.

Reactor systems configured to pyrolyze and activate carbon-containingfeedstocks, and introduce halogenated compound(s) and/or salts, will nowbe described in further detail.

In some embodiments, the reactor system is configured to carry out acontinuous process for producing activated carbon (e.g., a halogenatedactivated carbon composition as disclosed herein). In such embodiments,the reactor system comprises:

(a) an optional dryer for drying the one or more co-products by removingat least a portion of moisture from the one or more co-products;

(b) one or more indirectly heated reaction zones for mechanicallycountercurrently contacting the one or more co-products with a vaporstream comprising a substantially inert gas and an activation agentcomprising at least one of water or carbon dioxide, to generate solids,condensable vapors, and non-condensable gases, wherein the condensablevapors and the non-condensable gases enter the vapor stream, wherein theone or more indirectly heated reaction zones includes an optional gasinlet;

(c) a vapor stream separator in operative communication with one or moreindirectly heated reaction zone for removing at least a portion of thevapor stream from the reaction zone to generate a separated vapor streamand for recycling at least a portion of the separated vapor stream, or athermally treated form thereof, to contact the one or more co-productsprior to step (b) and/or to convey to the gas inlet of the reactionzone(s); and

(d) an activated carbon recovery zone for recovering at least a portionof the solids from the reaction zone(s) as activated carbon.

It is noted that size reduction is a costly and energy-intensiveprocess. Pyrolyzed material can be sized with significantly less energyinput, i.e. it can be more energy efficient to reduce the particle sizeof the product instead of (or in addition to) the feedstock. This is anoption in the present disclosure because the process does not require afine starting material, and there is not necessarily any particle-sizereduction during processing. The present disclosure provides the abilityto process very large pieces of feedstock. Notably, some marketapplications of the activated carbon product actually require largesizes (e.g., on the order of centimeters), so that in some embodiments,large pieces are fed, produced, and sold. It should be appreciated that,while not necessary in all embodiments of this disclosure, smallersizing has resulted in higher fixed carbon numbers under similar processconditions and may be utilized in some applications that typically callfor small sized activated carbon products and/or higher fixed carboncontent.

When it is desired to produce a final carbonaceous biogenic activatedcarbon product that has structural integrity, such as in the form ofcylinders, there are at least two options in the context of thisdisclosure. First, the material produced from the process is collectedand then further process mechanically into the desired form. Forexample, the product is pressed or pelletized, with a binder. The secondoption is to utilize feed materials that generally possess the desiredsize and/or shape for the final product, and employ processing stepsthat do not destroy the basic structure of the feed material. In someembodiments, the feed and product have similar geometrical shapes, suchas spheres, cylinders, or cubes.

The ability to maintain the approximate shape of feed materialthroughout the process is beneficial when product strength is important.Also, this control avoids the difficulty and cost of pelletizing highfixed-carbon materials.

There are a large number of options as to intermediate input and output(purge or probe) streams of one or more phases present in any particularreactor, various mass and energy recycle schemes, various additives thatmay be introduced anywhere in the process, adjustability of processconditions including both reaction and separation conditions in order totailor product distributions, and so on. Zone or reactor-specific inputand output streams enable good process monitoring and control, such asthrough FTIR sampling and dynamic process adjustments.

As used herein, the term “zones” includes regions of space within asingle physical unit, physically separate units, or any combinationthereof. The demarcation of zones may relate to structure, such as thepresence of flights or distinct heating elements to provide heat toseparate zones. Alternatively, or additionally, in various embodiments,the demarcation of zones relates to function, such as at least: distincttemperatures, fluid flow patterns, solid flow patterns, and extent ofreaction. In a single batch reactor, “zones” are operating regimes intime, rather than in space. It will be appreciated that there are notnecessarily abrupt transitions from one zone to another zone.

All references to zone temperatures in this specification includetemperatures that may apply to the bulk solids present, or the gasphase, or the reactor walls (on the process side). It will be understoodthat there may be a temperature gradient in each zone, both axially andradially, as well as temporally (i.e., following start-up or due totransients). Thus, references to zone temperatures may be references toaverage temperatures or other effective temperatures that may influencethe actual kinetics. Temperatures may be directly measured bythermocouples or other temperature probes, or indirectly measured orestimated by other means.

Various flow patterns may be desired or observed. With chemicalreactions and simultaneous separations involving multiple phases inmultiple zones, the fluid dynamics can be quite complex. Typically, theflow of solids may approach plug flow (well-mixed in the radialdimension) while the flow of vapor may approach fully mixed flow (fasttransport in both radial and axial dimensions). Multiple inlet andoutlet ports for vapor may contribute to overall mixing.

An optional step of separating at least a portion of the condensablevapors and at least a portion of the non-condensable gases from the hotpyrolyzed solids may be accomplished in the reactor itself, or using adistinct separation unit. A substantially inert sweep gas may beintroduced into one or more of the zones. Condensable vapors andnon-condensable gases are then carried away from the zone (s) in thesweep gas.

The sweep gas may be N₂, Ar, CO, CO₂, H₂, H₂O, CH₄, other lighthydrocarbons, or combinations thereof, for example. The sweep gas mayfirst be preheated prior to introduction, or cooled if it is obtainedfrom a heated source, to provide the sweep gas at a desired temperature.

The sweep gas more thoroughly removes volatile components, by enablingremoval from the system before they can condense or further react. Thesweep gas allows volatiles to be removed at higher rates than would beattained merely from volatilization at a given process temperature. Or,use of the sweep gas allows milder temperatures to be used to remove acertain quantity of volatiles. The reason the sweep gas improves thevolatiles removal is that the mechanism of separation is not merelyrelative volatility but rather liquid/vapor phase disengagement assistedby the sweep gas. The sweep gas can both reduce mass-transferlimitations of volatilization as well as reduce thermodynamiclimitations by continuously depleting a given volatile species, to causemore of it to vaporize to attain thermodynamic equilibrium.

It is important to remove gases laden with volatile organic carbon fromsubsequent processing stages, in order to produce a product with highfixed carbon. Without removal, the volatile carbon can adsorb or absorbonto the pyrolyzed solids, thereby requiring additional energy (cost) toachieve a purer form of carbon which may be desired. By removing vaporsquickly, it is also speculated that porosity may be enhanced in thepyrolyzing solids.

In certain embodiments, the sweep gas in conjunction with a relativelylow process pressure, such as atmospheric pressure, provides for fastvapor removal without large amounts of inert gas necessary.

In some embodiments, the sweep gas flows countercurrent to the flowdirection of feedstock. In other embodiments, the sweep gas flowscocurrent to the flow direction of feedstock. In some embodiments, theflow pattern of solids approaches plug flow while the flow pattern ofthe sweep gas, and gas phase generally, approaches fully mixed flow inone or more zones.

The sweep may be performed in any one or more of the zones. In someembodiments, the sweep gas is introduced into the cooling zone andextracted (along with volatiles produced) from the cooling and/orpyrolysis zones. In some embodiments, the sweep gas is introduced intothe pyrolysis zone and extracted from the pyrolysis and/or preheatingzones. In some embodiments, the sweep gas is introduced into thepreheating zone and extracted from the pyrolysis zone. In these or otherembodiments, the sweep gas may be introduced into each of thepreheating, pyrolysis, and cooling zones and also extracted from each ofthe zones.

The sweep gas may be introduced continuously, especially when the solidsflow is continuous. When the pyrolysis reaction is operated as a batchprocess, the sweep gas may be introduced after a certain amount of time,or periodically, to remove volatiles. Even when the pyrolysis reactionis operated continuously, the sweep gas may be introducedsemi-continuously or periodically, if desired, with suitable valves andcontrols.

The volatiles-containing sweep gas may exit from the one or more zones,and may be combined if obtained from multiple zones. The resulting gasstream, containing various vapors, may then be fed to a process gasheater for control of air emissions. Any known thermal-oxidation unitmay be employed. In some embodiments, the process gas heater is fed withnatural gas and air, to reach sufficient temperatures for substantialdestruction of volatiles contained therein.

The effluent of the process gas heater will be a hot gas streamcomprising water, carbon dioxide, and nitrogen. This effluent stream maybe purged directly to air emissions, if desired. In some embodiments,the energy content of the process gas heater effluent is recovered, suchas in a waste-heat recovery unit. The energy content may also berecovered by heat exchange with another stream (such as the sweep gas).The energy content may be utilized by directly or indirectly heating, orassisting with heating, a unit elsewhere in the process, such as thedryer or the reactor. In some embodiments, essentially all of theprocess gas heater effluent is employed for indirect heating (utilityside) of the dryer. The process gas heater may employ other fuels thannatural gas.

Carbonaceous solids may be introduced into a cooler. In someembodiments, solids are collected and simply allowed to cool at slowrates. If the carbonaceous solids are reactive or unstable in air, itmay be desirable to maintain an inert atmosphere and/or rapidly cool thesolids to, for example, a temperature less than 40° C., such as ambienttemperature. In some embodiments, a water quench is employed for rapidcooling. In some embodiments, a fluidized-bed cooler is employed. A“cooler” should be broadly construed to also include containers, tanks,pipes, or portions thereof.

In some embodiments, the process further comprises operating the coolerto cool the warm pyrolyzed solids with steam, thereby generating thecool pyrolyzed solids and superheated steam; wherein the drying iscarried out, at least in part, with the superheated steam derived fromthe cooler. Optionally, the cooler may be operated to first cool thewarm pyrolyzed solids with steam to reach a first cooler temperature,and then with air to reach a second cooler temperature, wherein thesecond cooler temperature is lower than the first cooler temperature andis associated with a reduced combustion risk for the warm pyrolyzedsolids in the presence of the air.

Following cooling to ambient conditions, the carbonaceous solids may berecovered and stored, conveyed to another site operation, transported toanother site, or otherwise disposed, traded, or sold. The solids may befed to a unit to reduce particle size. A variety of size-reduction unitsare known in the art, including crushers, shredders, grinders,pulverizers, jet mills, pin mills, and ball mills.

Screening or some other means for separation based on particle size maybe included. The screening may be upstream or downstream of grinding, ifpresent. A portion of the screened material (e.g., large chunks) may bereturned to the grinding unit. The small and large particles may berecovered for separate downstream uses. In some embodiments, cooledpyrolyzed solids are ground into a fine powder, such as a pulverizedcarbon or activated carbon product or increased strength.

Various additives may be introduced throughout the process, before,during, or after any step disclosed herein. The additives may be broadlyclassified as process additives, selected to improve process performancesuch as carbon yield or pyrolysis time/temperature to achieve thedesired carbon purity; and product additives, selected to improve one ormore properties of the biogenic activated carbon, or a downstreamproduct incorporating the reagent. Certain additives may provideenhanced process and product characteristics, such as overall yield ofbiogenic activated carbon product compared to the amount of biomassfeedstock. In some embodiments, additives as discussed below refer tohalogenated compounds and/or salts. In these or other embodiments,additives are incorporated into the halogenated activated carbon inaddition to the halogenated compounds and/or salts.

The additive may be added at any suitable time during the entireprocess. For example and without limitation, the additive may be addedbefore, during or after a feedstock drying step; before, during or aftera feedstock deaerating step; before, during or after a combustion step;before, during or after a pyrolysis step; before, during or after aseparation step; before, during or after any cooling step; before,during or after a biogenic activated carbon recovery step; before,during or after a pulverizing step; before, during or after a sizingstep; and/or before, during or after a packaging step. Additives may beincorporated at or on feedstock supply facilities, transport trucks,unloading equipment, storage bins, conveyors (including open or closedconveyors), dryers, process heaters, or any other units. Additives maybe added anywhere into the pyrolysis process itself, using suitablemeans for introducing additives. Additives may be added aftercarbonization, or even after pulverization, if desired.

In some embodiments, an additive is selected from a metal, a metaloxide, a metal hydroxide, or a combination thereof. For example anadditive may be selected from, but is by no means limited to, magnesium,manganese, aluminum, nickel, chromium, silicon, boron, cerium,molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride,iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

In some embodiments, an additive is selected from an acid, a base, or asalt thereof. For example an additive may be selected from, but is by nomeans limited to, sodium hydroxide, potassium hydroxide, magnesiumoxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassiumpermanganate, organic acids (e.g., citric acid), or combinationsthereof.

In some embodiments, an additive is selected from a metal halide. Metalhalides are compounds between metals and halogens (fluorine, chlorine,bromine, iodine, and astatine). The halogens can form many compoundswith metals. Metal halides are generally obtained by direct combination,or more commonly, neutralization of basic metal salt with a hydrohalicacid. In some embodiments, an additive is selected from iron halide(FeX₂ and/or FeX₃), iron chloride (FeCl₂ and/or FeCl₃), iron bromide(FeBr₂ and/or FeBr₃), or hydrates thereof, and any combinations thereof.

In some embodiments, an additive is selected from alkali metals oralkali metal-containing compounds such as those containing lithium,sodium, potassium, rubidium, caesium or francium. In some of theseembodiments, the carbon/metal compound can stores or transfer energy.

In some embodiments, a biogenic activated carbon composition comprises,on a dry basis:

55 wt % or more total carbon;

15 wt % or less hydrogen;

1 wt % or less nitrogen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur;

an additive selected from an acid, a base, a salt, a metal, a metaloxide, a metal hydroxide, a metal halide, iodine, an iodine compound, ora combination thereof.

In some embodiments, the additive comprises iodine or an iodinecompound, or a combination of iodine and one or more iodine compounds.When the additive comprises iodine, it may be present in the biogenicactivated carbon composition as absorbed or intercalated molecular I₂,as physically or chemically adsorbed molecular I₂, as absorbed orintercalated atomic I, as physically or chemically adsorbed atomic I, orany combination thereof.

When the additive comprises one or more iodine compounds, they may beselected from the group consisting of iodide ion, hydrogen iodide, aniodide salt, a metal iodide, ammonium iodide, an iodine oxide, triiodideion, a triiodide salt, a metal triiodide, ammonium triiodide, iodateion, an iodate salt, a polyiodide, iodoform, iodic acid, methyl iodide,an iodinated hydrocarbon, periodic acid, orthoperiodic acid,metaperiodic acid, and combinations, salts, acids, bases, or derivativesthereof.

In some embodiments, the additive comprises iodine or an iodinecompound, or a combination of iodine and one or more iodine compounds,optionally dissolved in a solvent. Various solvents for iodine or iodinecompounds are known in the art. For example, alkyl halides such as (butnot limited to) n-propyl bromide or n-butyl iodide may be employed.Alcohols such as methanol or ethanol may be used. In some embodiments, atincture of iodine may be employed to introduce the additive into thecomposition.

In some embodiments, the additive comprises iodine that is introduced asa solid that sublimes to iodine vapor for incorporation into thebiogenic activated carbon composition. At room temperature, iodine is asolid. Upon heating, the iodine sublimes into a vapor. Thus, solidiodine particles may be introduced into any stream, vessel, pipe, orcontainer (e.g. a barrel or a bag) that also includes the biogenicactivated carbon composition. Upon heating the iodine particles willsublime, and the I₂ vapor can penetrate into the carbon particles, thusincorporating iodine as an additive on the surface of the particles andpotentially within the particles.

In one embodiment, the present disclosure provides a method of using ahalogenated activated carbon composition to reduce emissions, the methodcomprising:

(a) providing activated-carbon particles comprising a halogenatedactivated carbon composition;

(b) providing a gas-phase emissions stream comprising at least oneselected contaminant;

(c) introducing the halogenated activated-carbon particles into thegas-phase emissions stream, to adsorb at least a portion of the selectedcontaminant onto the halogenated activated-carbon particles, therebygenerating contaminant-adsorbed halogenated activated carbon particleswithin the gas-phase emissions stream; and

(d) separating at least a portion of the contaminant-adsorbedhalogenated activated carbon particles from the gas-phase emissionsstream, to produce a contaminant-reduced gas-phase emissions stream.

The halogenated activated carbon composition may be any halogenatedactivated carbon composition described herein including, for example, ahalogenated activated carbon composition comprising, on a dry basis, atleast 85 wt % carbon; a halogenated compound; and a salt, wherein thehalogenated compound and the salt are present in a total amount of about0.1 wt % to about 15 wt %. The additive may be provided as part of theactivated-carbon particles. Alternatively, or additionally, the additivemay be introduced directly into the gas-phase emissions stream.

The additive may be selected from an acid, a base, a salt, a metal, ametal oxide, a metal hydroxide, a metal halide, iodine, an iodinecompound, or a combination thereof. In some embodiments, the additivecomprises iodine or an iodine compound, or a combination of iodine andone or more iodine compounds, optionally dissolved in a solvent.

In some embodiments, the selected contaminant is a metal, such as ametal selected from the group consisting of mercury, boron, selenium,arsenic, and any compound, salt, and mixture thereof. In someembodiments, the selected contaminant is a hazardous air pollutant or avolatile organic compound. In some embodiments, the selected contaminantis a non-condensable gas selected from the group consisting of nitrogenoxides, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfurdioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, andcombinations thereof.

In some embodiments, the contaminant-adsorbed halogenated activatedcarbon particles include, in absorbed, adsorbed, or reacted form, atleast one, two, three, or all contaminants selected from the groupconsisting of carbon dioxide, nitrogen oxides, mercury, and sulfurdioxide.

In some embodiments, the gas-phase emissions stream is derived fromcombustion of a fuel comprising the halogenated activated carboncomposition. In certain embodiments, the gas-phase emissions stream isderived from co-combustion of coal and the halogenated activated carboncomposition.

In some embodiments, the separating in step (d) comprises filtration,which may for example utilize fabric filters. In some embodiments,separating in step (d) comprises electrostatic precipitation. Scrubbing(including wet or dry scrubbing) may also be employed. Optionally, thecontaminant-adsorbed carbon particles may be treated to regenerate theactivated-carbon particles. In some embodiments, thecontaminant-adsorbed carbon particles are thermally oxidizedcatalytically or non-catalytically. The contaminant-adsorbed carbonparticles, or a regenerated form thereof, may be combusted to provideenergy and/or gasified to provide syngas.

In some embodiments, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to reduce mercuryemissions, the method comprising:

(a) providing halogenated activated-carbon particles comprising ahalogenated biogenic activated carbon composition;

(b) providing a gas-phase emissions stream comprising mercury;

(c) introducing the halogenated activated-carbon particles into thegas-phase emissions stream, to adsorb at least a portion of the mercuryonto the halogenated activated-carbon particles, thereby generatingmercury-adsorbed halogenated carbon particles within the gas-phaseemissions stream; and

(d) separating at least a portion of the mercury-adsorbed halogenatedcarbon particles from the gas-phase emissions stream using electrostaticprecipitation, to produce a mercury-reduced gas-phase emissions stream.

In one embodiment, the present disclosure provides a process for energyproduction, the process comprising:

(a) providing a carbon-containing feedstock comprising a halogenatedbiogenic activated carbon composition; and

-   -   (b) oxidizing the carbon-containing feedstock to generate energy        and a gas-phase emissions stream,

wherein the presence of the halogenated biogenic activated carboncomposition within the carbon-containing feedstock is effective toadsorb at least one contaminant produced as a byproduct of the oxidizingor derived from the carbon-containing feedstock, thereby reducingemissions of the contaminant, and

wherein the halogenated biogenic activated carbon composition comprises,on a dry basis, at least 85 wt % carbon; a halogenated compound; and asalt, wherein the halogenated compound and the salt are present in atotal amount of about 0.1 wt % to about 15 wt %.

In some embodiments, the contaminant, or a precursor thereof, iscontained within the carbon-containing feedstock. In some embodiments,the contaminant is produced as a byproduct of the oxidizing. Thecarbon-containing feedstock further comprises biomass, coal, or anothercarbonaceous feedstock, in various embodiments.

The selected contaminant may be a metal selected from the groupconsisting of mercury, boron, selenium, arsenic, and any compound, salt,and mixture thereof; a hazardous air pollutant; a volatile organiccompound; or a non-condensable gas selected from the group consisting ofnitrogen oxides, carbon monoxide, carbon dioxide, hydrogen sulfide,sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone,ammonia; and combinations thereof.

In some embodiments, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to purify a liquid,the method comprising:

(a) providing halogenated activated-carbon particles comprising abiogenic activated carbon composition;

(b) providing a liquid comprising at least one selected contaminant; and

(c) contacting the liquid with the halogenated activated-carbonparticles to adsorb at least a portion of the at least one selectedcontaminant onto the halogenated activated-carbon particles, therebygenerating contaminant-adsorbed halogenated carbon particles and acontaminant-reduced liquid.

The halogenated biogenic activated carbon may be any halogenatedactivated carbon composition described herein including, for example, ahalogenated biogenic activated carbon composition comprising, on a drybasis, at least 85 wt % carbon; a halogenated compound; and a salt,wherein the halogenated compound and the salt are present in a totalamount of about 0.1 wt % to about 15 wt %.

In some embodiments, the halogenated compound and/or the salt comprisesiodine as absorbed or intercalated molecular I₂, physically orchemically adsorbed molecular I₂, absorbed or intercalated atomic I,physically or chemically adsorbed atomic I, or a combination thereof.

In some embodiments, the halogenated compound and/or the salt comprisesan iodine-containing compound, such as (but not limited to) aniodine-containing compound is selected from the group consisting ofiodide ion, hydrogen iodide, an iodide salt, a metal iodide, ammoniumiodide, an iodine oxide, triiodide ion, a triiodide salt, a metaltriiodide, ammonium triiodide, iodate ion, an iodate salt, a polyiodide,iodoform, iodic acid, methyl iodide, an iodinated hydrocarbon, periodicacid, orthoperiodic acid, metaperiodic acid, and combinations, salts,acids, bases, or derivatives thereof.

The halogenated compound and/or the salt may be applied to wet or drybiomass feedstocks. The additives may be applied as a solid powder, aspray, a mist, a liquid, or a vapor. In some embodiments, thehalogenated compound and/or the salt may be introduced through sprayingof a liquid solution (such as an aqueous solution or in a solvent), orby soaking in tanks, bins, bags, or other containers.

In certain embodiments, dip pretreatment is employed wherein the solidfeedstock is dipped into a bath comprising the halogenated compoundand/or the salt, either batchwise or continuously, for a time sufficientto allow penetration of the halogenated compound and/or the salt intothe solid feed material.

In some embodiments, the process for producing a halogenated biogenicactivated carbon further comprises a step of sizing (e.g., sorting,screening, classifying, etc.) the warm or cool pyrolyzed solids to formsized pyrolyzed solids. The sized pyrolyzed solids can then be used inapplications which call for an activated carbon product having a certainparticle size characteristic.

The throughput, or process capacity, may vary widely from smalllaboratory-scale units to full commercial-scale biorefineries, includingany pilot, demonstration, or semi-commercial scale. In variousembodiments, the process capacity is at least about 1 kg/day, 10 kg/day,100 kg/day, 1 ton/day (all tons are metric tons), 10 tons/day, 100tons/day, 500 tons/day, 1000 tons/day, 2000 tons/day, or higher.

Solid, liquid, and gas streams produced or existing within the processcan be independently recycled, passed to subsequent steps, orremoved/purged from the process at any point.

Gas outlets (probes) allow precise process monitoring and control acrossvarious stages of the process, up to and potentially including allstages of the process. Precise process monitoring would be expected toresult in yield and efficiency improvements, both dynamically as well asover a period of time when operational history can be utilized to adjustprocess conditions.

In some embodiments, a reaction gas probe is disposed in operablecommunication a process zone. Such a reaction gas probe may be useful toextract gases and analyze them, in order to determine extent ofreaction, pyrolysis selectivity, or other process monitoring. Then,based on the measurement, the process may be controlled or adjusted inany number of ways, such as by adjusting feed rate, rate of inert gassweep, temperature (of one or more zones), pressure (of one or morezones), additives, and so on.

As intended herein, “monitor and control” via reaction gas probes shouldbe construed to include any one or more sample extractions via reactiongas probes, and optionally making process or equipment adjustments basedon the measurements, if deemed necessary or desirable, using well-knownprinciples of process control (feedback, feedforward,proportional-integral-derivative logic, etc.).

A reaction gas probe may be configured to extract gas samples in anumber of ways. For example, a sampling line may have a lower pressurethan the pyrolysis reactor pressure, so that when the sampling line isopened an amount of gas can readily be extracted from pyrolysis zone.The sampling line may be under vacuum, such as when the pyrolysis zoneis near atmospheric pressure. Typically, a reaction gas probe will beassociated with one gas output, or a portion thereof (e.g., a line splitfrom a gas output line).

In some embodiments, both a gas input and a gas output are utilized as areaction gas probe by periodically introducing an inert gas into a zone,and pulling the inert gas with a process sample out of the gas output(“sample sweep”). Such an arrangement could be used in a zone that doesnot otherwise have a gas inlet/outlet for the substantially inert gasfor processing, or, the reaction gas probe could be associated with aseparate gas inlet/outlet that is in addition to process inlets andoutlets. A sampling inert gas that is introduced and extractedperiodically for sampling (in embodiments that utilize sample sweeps)could even be different than the process inert gas, if desired, eitherfor reasons of accuracy in analysis or to introduce an analyticaltracer.

For example, acetic acid concentration in the gas phase may be measuredusing a gas probe to extract a sample, which is then analyzed using asuitable technique (such as gas chromatography, GC; mass spectroscopy,MS; GC-MS, or Fourier-Transform Infrared Spectroscopy, FTIR). CO and/orCO₂ concentration in the gas phase could be measured and used as anindication of the pyrolysis selectivity toward gases/vapors, forexample. Terpene concentration in the gas phase could be measured andused as an indication of the pyrolysis selectivity toward liquids, andso on.

In some embodiments, the system further comprises at least oneadditional gas probe disposed in operable communication with the coolingzone, or with the drying zone (if present) or the preheating zone (ifpresent).

A gas probe for the cooling zone could be useful to determine the extentof any additional chemistry taking place in the cooling zone, forexample. A gas probe in the cooling zone could also be useful as anindependent measurement of temperature (in addition, for example, to athermocouple disposed in the cooling zone). This independent measurementmay be a correlation of cooling temperature with a measured amount of acertain species. The correlation could be separately developed, or couldbe established after some period of process operation.

A gas probe for the drying zone could be useful to determine the extentof drying, by measuring water content, for example. A gas probe in thepreheating zone could be useful to determine the extent of any mildpyrolysis taking place, for example.

In some embodiments of the disclosure, the system further includes aprocess gas heater disposed in operable communication with the outlet atwhich condensable vapors and non-condensable gases are removed. Theprocess gas heater can be configured to receive a separate fuel (such asnatural gas) and an oxidant (such as air) into a combustion chamber,adapted for combustion of the fuel and at least a portion of thecondensable vapors. Certain non-condensable gases may also be oxidized,such as CO or CH₄, to CO₂.

When a process gas heater is employed, the system may include a heatexchanger disposed between the process gas heater and the dryer,configured to utilize at least some of the heat of the combustion forthe dryer. This embodiment can contribute significantly to the overallenergy efficiency of the process.

In some embodiments, the system further comprises a material enrichmentunit, disposed in operable communication with a cooler, configured forcombining condensable vapors, in at least partially condensed form, withthe solids. The material enrichment unit may increase the carbon contentof the halogenated biogenic activated carbon.

In certain embodiments, the combustion products include carbon monoxide,the process further comprising utilizing the carbon monoxide as a fuelwithin the process or for another process. For example, the CO may beused as a direct or indirect fuel to a pyrolysis unit.

The system may further include a separate pyrolysis zone adapted tofurther pyrolyze the halogenated biogenic activated carbon to furtherincrease its carbon content. The separate pyrolysis zone may be arelatively simply container, unit, or device, such as a tank, barrel,bin, drum, tote, sack, or roll-off.

The overall system may be at a fixed location, or it may be madeportable. The system may be constructed using modules which may besimply duplicated for practical scale-up. The system may also beconstructed using economy-of-scale principles, as is well-known in theprocess industries.

In some embodiments, the process for producing a halogenated biogenicactivated carbon further comprises a step of sizing (e.g., sorting,screening, classifying, etc.) the warm or cool pyrolyzed solids to formsized pyrolyzed solids. The sized pyrolyzed solids can then be used inapplications which call for a halogenated activated carbon producthaving a certain particle size characteristic.

In some embodiments, the halogenated biogenic activated carbon comprisesat least about 55 wt. % total carbon on a dry basis, for example atleast 55 wt. %, at least 60 wt. %, at least 65 wt. %, at least 70 wt %,at least 75 wt. %, at least 80 wt %, at least 85 wt. %, at least 90 wt%, at least 95 wt %, at least 96 wt %, at least 97 wt %, at least 98 wt%, or at least 99 wt % total carbon on a dry basis. The total carbonincludes at least fixed carbon, and may further include carbon fromvolatile matter. In some embodiments, carbon from volatile matter isabout at least 5%, at least 10%, at least 25%, or at least 50% of thetotal carbon present in the biogenic activated carbon. Fixed carbon maybe measured using ASTM D3172, while volatile carbon may be estimatedusing ASTM D3175, for example.

Halogenated biogenic activated carbon according to the presentdisclosure may comprise about 0 wt % to about 8 wt % hydrogen. In someembodiments, biogenic activated carbon comprises greater than about 0.5wt % hydrogen, for example about 0.6 wt %, about 0.7 wt %, about 0.8 wt%, about 0.9 wt %, about 1 wt %, about 1.2 wt %, about 1.4 wt %, about1.6 wt %, about 1.8 wt %, about 2 wt %, about 2.2 wt %, about 2.4 wt %,about 2.6 wt %, about 2.8 wt %, about 3 wt %, about 3.2 wt %, about 3.4wt %, about 3.6 wt %, about 3.8 wt %, about 4 wt %, or greater thanabout 4 wt % hydrogen. The hydrogen content of halogenated biogenicactivated carbon may be determined by any suitable method known in theart, for example by the combustion analysis procedure outlined in ASTMD5373. In some embodiments, halogenated biogenic activated carbon has ahydrogen content that is greater than the hydrogen content of activatedcarbon derived from fossil fuel sources. Typically, fossil fuel basedactivated carbon products have less than 1 wt % hydrogen, for exampleabout 0.6 wt % hydrogen. In some embodiments, the characteristics of ahalogenated activated carbon product can be optimized by blending anamount of a fossil fuel based activated carbon product (i.e., with avery low hydrogen content) with a suitable amount of a halogenatedbiogenic activated carbon product having a hydrogen content greater thanthat of the fossil fuel based activated carbon product.

The halogenated biogenic activated carbon may comprise about 10 wt % orless, such as about 5 wt % or less, hydrogen on a dry basis. Thebiogenic activated carbon product may comprise about 1 wt % or less,such as about 0.5 wt % or less, nitrogen on a dry basis. The biogenicactivated carbon product may comprise about 0.5 wt % or less, such asabout 0.2 wt % or less, phosphorus on a dry basis. The biogenicactivated carbon product may comprise about 0.2 wt % or less, such asabout 0.1 wt % or less, sulfur on a dry basis.

In certain embodiments, the halogenated biogenic activated carbonincludes oxygen, such as up to 20 wt % oxygen, for example about 0.2 wt%, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt%, about 5 wt %, about 6 wt %, about 7 wt %, about 7.5 wt %, about 8 wt%, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about18 wt %, about 19 wt %, or about 20 wt % oxygen. The presence of oxygenmay be beneficial in the activated carbon for certain applications, suchas mercury capture, especially in conjunction with the presence of ahalogen (such as chlorine or bromine). In some embodiments, biogenicactivated carbon has a oxygen content that is greater than the oxygencontent of activated carbon derived from fossil fuel sources. Typically,fossil fuel based activated carbon products have less than 10 wt %oxygen, for example about 7 wt % oxygen or about 0.3 wt % oxygen. Insome embodiments, the characteristics of an activated carbon product canbe optimized by blending an amount of a fossil fuel based activatedcarbon product (i.e., with a very low oxygen content) with a suitableamount of a biogenic activated carbon product having an oxygen contentgreater than that of the fossil fuel based activated carbon product.

Carbon, hydrogen, and nitrogen may be measured using ASTM D5373 forultimate analysis, for example. Oxygen may be estimated using ASTMD3176, for example. Sulfur may be measured using ASTM D3177, forexample.

Certain embodiments provide reagents with little or essentially nohydrogen (except from any moisture that may be present), nitrogen,phosphorus, or sulfur, and are substantially carbon plus any ash andmoisture present, plus the halogenated compound and/or the salt.Therefore, some embodiments provide a material with up to and including100% carbon, on a dry, ash-free, and halogen/salt-free basis.

Various amounts of non-combustible matter, such as ash, may be presentin the final product. The halogenated biogenic activated carbon maycomprise about 10 wt % or less, such as about 5 wt %, about 2 wt %,about 1 wt % or less than about 1 wt % of non-combustible matter on adry basis. In certain embodiments, the reagent includes little ash, oreven essentially no ash or other non-combustible matter. Therefore, someembodiments provide essentially pure carbon, including 100% carbon, on adry basis.

Various amounts of moisture may be present. On a total mass basis, thehalogenated biogenic activated carbon may comprise at least 1 wt %, atleast 2 wt %, at least 5 wt %, at least 10 wt %, at least 15 wt %, atleast 25 wt %, at least 35 wt %, at least 50 wt %, or more than 50 wt %of moisture. As intended herein, “moisture” is to be construed asincluding any form of water present in the biogenic activated carbonproduct, including absorbed moisture, adsorbed water molecules, chemicalhydrates, and physical hydrates. The equilibrium moisture content mayvary at least with the local environment, such as the relative humidity.Also, moisture may vary during transportation, preparation for use, andother logistics. Moisture may be measured by any suitable method knownin the art, including ASTM D3173, for example.

The halogenated biogenic activated carbon may have various “energycontent” which for present purposes means the energy density based onthe higher heating value associated with total combustion of thebone-dry reagent. For example, the halogenated biogenic activated carbonmay possess an energy content of about at least 11,000 Btu/lb, at least12,000 Btu/lb, at least 13,000 Btu/lb, at least 14,000 Btu/lb, or atleast 15,000 Btu/lb. In certain embodiments, the energy content isbetween about 14,000-15,000 Btu/lb. The energy content may be measuredby any suitable method known in the art, including ASTM D5865, forexample.

The halogenated biogenic activated carbon may be formed into a powder,such as a coarse powder or a fine powder. For example, the reagent maybe formed into a powder with an average mesh size of about 200 mesh,about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4mesh, or about 2 mesh, in embodiments. In some embodiments, thehalogenated biogenic activated carbon has an average particle size of upto about 500 μm, for example less than about 10 μm, about 10 μm, about25 μm, about 50 μm, about 75 μm, about 100 μm, about 200 μm, about 300μm, about 400 μm, or about 500 μm.

The halogenated biogenic activated carbon may be produced as powderactivated carbon, which generally includes particles with a sizepredominantly less than 0.21 mm (70 mesh). The halogenated biogenicactivated carbon may be produced as granular activated carbon, whichgenerally includes irregularly shaped particles with sizes ranging from0.2 mm to 5 mm. The halogenated biogenic activated carbon may beproduced as pelletized activated carbon, which generally includesextruded and cylindrically shaped objects with diameters from 0.8 mm to5 mm.

In some embodiments, the halogenated biogenic activated carbon is formedinto structural objects comprising pressed, binded, or agglomeratedparticles. The starting material to form these objects may be a powderform of the reagent, such as an intermediate obtained by particle-sizereduction. The objects may be formed by mechanical pressing or otherforces, optionally with a binder or other means of agglomeratingparticles together.

Following formation from pyrolysis, the halogenated biogenic activatedcarbon may be pulverized to form a powder. “Pulverization” in thiscontext is meant to include any sizing, milling, pulverizing, grinding,crushing, extruding, or other primarily mechanical treatment to reducethe average particle size. The mechanical treatment may be assisted bychemical or electrical forces, if desired. Pulverization may be a batch,continuous, or semi-continuous process and may be carried out at adifferent location than that of formation of the pyrolyzed solids, insome embodiments.

In some embodiments, the halogenated biogenic activated carbon isproduced in the form of structural objects whose structure substantiallyderives from the feedstock. For example, feedstock chips may produceproduct chips of halogenated biogenic activated carbon. Or, feedstockcylinders may produce halogenated biogenic activated carbon cylinders,which may be somewhat smaller but otherwise maintain the basic structureand geometry of the starting material.

A halogenated biogenic activated carbon according to the presentdisclosure may be produced as, or formed into, an object that has aminimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm,7 cm, 8 cm, 9 cm, 10 cm, or higher. In various embodiments, the minimumdimension or maximum dimension can be a length, width, or diameter.

In some embodiments, the present disclosure relates to the incorporationof additives into the process, into the product, or both. In someembodiments, the halogenated biogenic activated carbon includes at leastone process additive incorporated during the process. In these or otherembodiments, the halogenated activated carbon includes at least oneproduct additive introduced to the halogenated activated carbonfollowing the process.

In some embodiments, the present disclosure relates to the incorporationof additives into the process, into the product, or both. In someembodiments, the halogenated biogenic activated carbon includes at leastone process additive incorporated during the process. In these or otherembodiments, the reagent includes at least one product additiveintroduced to the reagent following the process.

In some embodiments, a halogenated biogenic activated carbon comprises,on a dry basis:

55 wt % or more total carbon;

a halogenated compound and a salt present in a total amount of about 0.2wt % to about 20 wt %;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

optionally from 0.5 wt % to 10 wt % oxygen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from a metal, a metal oxide, a metal hydroxide, ora combination thereof.

The additive may be selected from, but is by no means limited to, ironchloride, iron bromide, magnesium, manganese, aluminum, nickel,chromium, silicon, magnesium oxide, dolomite, dolomitic lime, fluorite,fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

In some embodiments, a halogenated biogenic activated carbon comprises,on a dry basis:

55 wt % or more total carbon;

a halogenated compound and a salt present in a total amount of about 0.2wt % to about 20 wt %;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

optionally from 0.5 wt % to 10 wt % oxygen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur; and

an additive selected from an acid, a base, or a salt thereof.

The additive may be selected from, but is by no means limited to, sodiumhydroxide, potassium hydroxide, magnesium oxide, sodium silicate,potassium permanganate, organic acids (e.g., citric acid), orcombinations thereof.

In certain embodiments, a biogenic activated carbon comprises, on a drybasis:

55 wt % or more total carbon;

a halogenated compound and a salt present in a total amount of about 0.2wt % to about 20 wt %;

5 wt % or less hydrogen;

1 wt % or less nitrogen;

optionally from 0.5 wt % to 10 wt % oxygen;

0.5 wt % or less phosphorus;

0.2 wt % or less sulfur;

a first additive selected from a metal, metal oxide, metal hydroxide, ora combination thereof; and

a second additive selected from an acid, a base, or a salt thereof,

wherein the first additive is different from the second additive.

The first additive may be selected from magnesium, manganese, aluminum,nickel, chromium, silicon, magnesium oxide, dolomite, dolomitic lime,bentonite, calcium oxide, lime, or combinations thereof, while thesecond additive may be independently selected from sodium hydroxide,potassium hydroxide, magnesium oxide, sodium silicate, potassiumpermanganate, organic acids (e.g., citric acid), or combinationsthereof.

In one embodiment, a halogenated biogenic activated carbon consistentwith the present disclosure consists essentially of, on a dry basis,carbon, hydrogen, nitrogen, oxygen, phosphorus, sulfur, non-combustiblematter, and an additive selected from the group consisting of magnesium,manganese, aluminum, nickel, chromium, silicon, magnesium oxide,dolomite, dolomitic lime, bentonite, calcium oxide, lime, andcombinations thereof.

In one embodiment, a halogenated biogenic activated carbon consistentwith the present disclosure consists essentially of, on a dry basis,carbon, hydrogen, nitrogen, oxygen, phosphorus, sulfur, non-combustiblematter, a halogenated compound, a salt, and an additive selected fromthe group consisting of sodium hydroxide, potassium hydroxide, magnesiumoxide, sodium silicate, and combinations thereof.

The amount of additive (or total additives) may vary widely, such asfrom about 0.01 wt % to about 25 wt %, including about 0.1 wt %, about 1wt %, about 5 wt %, about 10 wt %, or about 20 wt % on a dry basis. Itwill be appreciated then when relatively large amounts of additives areincorporated, such as higher than about 1 wt %, there will be areduction in energy content calculated on the basis of the totalactivated carbon weight (inclusive of additives). Still, in variousembodiments, the halogenated biogenic activated carbon with additive(s)may possess an energy content of about at least 11,000 Btu/lb, at least12,000 Btu/lb, at least 13,000 Btu/lb, at least 14,000 Btu/lb, or atleast 15,000 Btu/lb, when based on the entire weight of the biogenicactivated carbon (including the additive(s)).

The above discussion regarding product form applies also to embodimentsthat incorporate additives. In fact, certain embodiments incorporateadditives as binders or other modifiers to enhance final properties fora particular application.

In some embodiments, the majority of carbon contained in the halogenatedbiogenic activated carbon is classified as renewable carbon. In someembodiments, substantially all of the carbon is classified as renewablecarbon. There may be certain market mechanisms (e.g., RenewableIdentification Numbers, tax credits, etc.) wherein value is attributedto the renewable carbon content within the halogenated biogenicactivated carbon. In some embodiments, the additive itself is derivedfrom biogenic sources or is otherwise classified as derived from arenewable carbon source. For example, some organic acids such as citricacid are derived from renewable carbon sources. Thus, in someembodiments, the carbon content of a halogenated biogenic activatedcarbon consists of, consists essentially of, or consists of renewablecarbon. For example, a fully biogenic halogenated activated carbonformed by methods as disclosed herein consist of, consist essentiallyof, or consist substantially of (a) pyrolyzed solids derived solely frombiomass from renewable carbon sources, (b) a halogenated compoundderived from renewable sources, and (c) a salt derived from renewablesources.

The halogenated biogenic activated carbon compositions produced asdescribed herein are useful for a wide variety of carbonaceous products.In embodiments, a product includes any of the halogenated biogenicactivated carbons that may be obtained by the disclosed processes, orthat are described in the compositions set forth herein, or anyportions, combinations, or derivatives thereof.

Generally speaking, the halogenated biogenic activated carbons may becombusted to produce energy (including electricity and heat); partiallyoxidized or steam-reformed to produce syngas; utilized for theiradsorptive or absorptive properties; utilized for their reactiveproperties during metal refining (such as reduction of metal oxides) orother industrial processing; or utilized for their material propertiesin carbon steel and various other metal alloys. Essentially, thehalogenated biogenic activated carbons may be utilized for any marketapplication of carbon-based commodities or advanced materials (e.g.,graphene), including specialty uses to be developed.

Halogenated biogenic activated carbon compositions prepared according tothe processes disclosed herein have the same or better characteristicsas traditional fossil fuel-based activated carbon. In some embodiments,halogenated biogenic activated carbon has a surface area that iscomparable to, equal to, or greater than surface area associated withfossil fuel-based activated carbon. In some embodiments, halogenatedbiogenic activated carbon can control pollutants as well as or betterthan traditional activated carbon products. In some embodiments,halogenated biogenic activated carbon has an inert material (e.g., ash)level that is comparable to, equal to, or less than an inert material(e.g., ash) level associated with a traditional activated carbonproduct. In some embodiments, halogenated biogenic activated carbon hasa particle size and/or a particle size distribution that is comparableto, equal to, greater than, or less than a particle size and/or aparticle size distribution associated with a traditional activatedcarbon product. In some embodiments, a halogenated biogenic activatedcarbon product has a particle shape that is comparable to, substantiallysimilar to, or the same as a particle shape associated with atraditional activated carbon product. In some embodiments, a halogenatedbiogenic activated carbon product has a particle shape that issubstantially different than a particle shape associated with atraditional activated carbon product. In some embodiments, a halogenatedbiogenic activated carbon product has a pore volume that is comparableto, equal to, or greater than a pore volume associated with atraditional activated carbon product. In some embodiments, a halogenatedbiogenic activated carbon product has pore dimensions that arecomparable to, substantially similar to, or the same as pore dimensionsassociated with a traditional activated carbon product. In someembodiments, a halogenated biogenic activated product has an attritionresistance of particles value that is comparable to, substantiallysimilar to, or the same as an attrition resistance of particles valueassociated with a traditional activated carbon product. In someembodiments, a halogenated biogenic activated carbon product has ahardness value that is comparable to, substantially similar to, or thesame as a hardness value associated with a traditional activated carbonproduct. In some embodiments, a halogenated biogenic activated carbonproduct has a hardness value that is comparable to, substantially lessthan, or less than a hardness value associated with a traditionalactivated carbon product. In some embodiments, a halogenated biogenicactivated carbon product has a bulk density value that is comparable to,substantially similar to, or the same as a bulk density value associatedwith a traditional activated carbon product. In some embodiments, ahalogenated biogenic activated carbon product has a bulk density valuethat is comparable to, substantially less than, or less than a bulkdensity value associated with a traditional activated carbon product. Insome embodiments, a halogenated biogenic activated carbon product has anabsorptive capacity that is comparable to, substantially similar to, orthe same as an absorptive capacity associated with a traditionalactivated carbon product.

Prior to suitability or actual use in any product applications, thedisclosed halogenated biogenic activated carbons may be analyzed,measured, and optionally modified (such as through additives) in variousways. Some properties of potential interest, other than chemicalcomposition and energy content, include density, particle size, surfacearea, microporosity, absorptivity, adsorptivity, binding capacity,reactivity, desulfurization activity, basicity, hardness, and IodineNumber.

In one embodiment, the present disclosure provides various halogenatedactivated carbon products. Halogenated activated carbon is used in awide variety of liquid and gas-phase applications, including watertreatment, air purification, solvent vapor recovery, food and beverageprocessing, sugar and sweetener refining, automotive uses, andpharmaceuticals. For halogenated activated carbon, key productattributes may include particle size, shape, and composition; surfacearea, pore volume and pore dimensions, particle-size distribution, thechemical nature of the carbon surface and interior, attrition resistanceof particles, hardness, bulk density, and adsorptive capacity.

The surface area of the halogenated biogenic activated carbon may varywidely. Exemplary surface areas range from about 400 m²/g to about 2000m²/g or higher, such as about 500 m²/g, 600 m²/g, 800 m²/g, 1000 m²/g,1200 m²/g, 1400 m²/g, 1600 m²/g, or 1800 m²/g. Surface area generallycorrelates to adsorption capacity.

The Iodine Number is a parameter used to characterize activated carbonperformance. The Iodine Number measures the degree of activation of thecarbon, and is a measure of micropore (e.g., 0-20 Å) content. It is animportant measurement for liquid-phase applications. Exemplary IodineNumbers for halogenated activated carbon products produced byembodiments of the disclosure include about 500, 600, 750, 900, 1000,1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200.

Other pore-related measurements include Methylene Blue, which measuresmesopore content (e.g., 20-500 Å); and Molasses Number, which measuresmesopore and macropore content (e.g., >500 Å), and Tannin Value, whichmeasures mesopore and macropore content. The pore-size distribution andpore volume are important to determine ultimate performance. A typicalbulk density for the halogenated biogenic activated carbon compositionsdisclosed herein is about 400 to 500 g/liter, such as about 450 g/liter.

In some embodiments, the disclosure provides a halogenated activatedcarbon product, wherein the product has a mesoporosity characterized bymesopore volume of at least about 0.5 cubic centimeters per gram ofactivated carbon product (cm³/g), such as a mesopore volume of at leastabout 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, or morecubic centimeters per gram. “Mesopores” are defined as pores with poresizes from 2 nm to 50 nm. Pores smaller than 2 nm are “micropores,” andpores larger than 50 nm are “macropores.”

In some embodiments, the disclosure provides a halogenated activatedcarbon product, wherein the product is characterized by a MolassesNumber of about 500 or greater, such as a Molasses Number of about 550,600, 650, 700, 750, 800, 850, 900, 950, 1000, 1030, 1060, or greater.The Molasses Number may be measured, for example, by Standard MethodCalgon TM-3.

In some embodiments, the disclosure provides a halogenated activatedcarbon product, wherein the product is characterized by a Tannin Valueof about 100 or less, such as a Tannin Value of about 75, 70, 65, 60,55, 50, 45, 40, 35, or less. The Tannin Value may be measured, forexample, by Standard Method AWWA B600-10.

In some embodiments, a halogenated activated carbon product has amesoporosity characterized by mesopore volume of at least about 0.5cubic centimeters per gram, a Molasses Number of about 500 or greater,and a Tannin Value of about 100 or less.

In certain embodiments, a halogenated activated carbon product has amesoporosity characterized by mesopore volume of at least about 0.7cubic centimeters per gram, a Molasses Number of about 1000 or greater,and a Tannin Value of about 35 or less.

The halogenated activated carbon product may be further characterized bya total pore volume of at least about 0.85 cubic centimeters per gram.The halogenated activated carbon product may be further characterized bya BET surface area of at least about 800 square meters per gram.

The halogenated activated carbon product may be further characterized byMIB/Geosmin removal or other suitable tests. For example, removal of MIBaccording to Standard Method AWWA B600-10 may be about 85%, 90%, 93%, orhigher. Removal of Geosmin according to Standard Method AWWA B600-10 maybe about 90%, 95%, 99%, or higher.

Hardness or Abrasion Number is measure of activated carbon's resistanceto attrition. It is an indicator of activated carbon's physicalintegrity to withstand frictional forces and mechanical stresses duringhandling or use. Some amount of hardness is desirable, but if thehardness is too high, excessive equipment wear can result. ExemplaryAbrasion Numbers, measured according to ASTM D3802, for halogenatedactivated carbon compositions disclosed herein range from about 1% togreater than about 99%, such as about 1%, about 5%, about 10%, about15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%,about 50%, about 55%, 60%, about 65%, about 70%, about 75%, about 80%,about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about99%, or greater than about 99%.

In some embodiments, an optimal range of hardness can be achieved inwhich the halogenated biogenic activated carbon is reasonably resistantto attrition but does not cause abrasion and wear in capital facilitiesthat process the halogenated activated carbon. This optimum is madepossible in some embodiments of this disclosure due to the selection offeedstock as well as processing conditions.

For example, it is known that coconut shells tend to produce AbrasionNumbers of 99% or higher, so coconut shells would be a less-than-optimalfeedstock for achieving optimum hardness. In some embodiments in whichthe downstream use can handle high hardness, the process of thisdisclosure may be operated to increase or maximize hardness to producehalogenated biogenic activated carbon products having an Abrasion Numberof about 75%, about 80%, about 85%, about 90%, about 95%, about 96%,about 97%, about 98%, about 99%, or greater than about 99%.

The halogenated biogenic activated carbon compositions provided by thepresent disclosure have a wide range of commercial uses. For example,without limitation, the halogenated biogenic activated carboncompositions may be utilized in emissions control, water purification,groundwater treatment, wastewater treatment, air stripper applications,PCB removal applications, odor removal applications, soil vaporextractions, manufactured gas plants, industrial water filtration,industrial fumigation, tank and process vents, pumps, blowers, filters,pre-filters, mist filters, ductwork, piping modules, adsorbers,absorbers, and columns, energy storage and capacitance.

In one embodiment, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to reduce emissions,the method comprising:

(a) providing halogenated activated carbon particles comprising abiogenic activated carbon composition;

(b) providing a gas-phase emissions stream comprising at least oneselected contaminant;

(c) introducing the activated carbon particles and the additive into thegas-phase emissions stream, to adsorb at least a portion of the selectedcontaminant onto the halogenated activated carbon particles, therebygenerating contaminant-adsorbed halogenated activated carbon particleswithin the gas-phase emissions stream; and

(d) separating at least a portion of the contaminant-adsorbed carbonparticles from the gas-phase emissions stream, to produce acontaminant-reduced gas-phase emissions stream.

A selected contaminant (in the gas-phase emissions stream) may be ametal, such as a metal is selected from the group consisting of mercury,boron, selenium, arsenic, and any compound, salt, and mixture thereof. Aselected contaminant may be a hazardous air pollutant, an organiccompound (such as a VOC), or a non-condensable gas, for example. In someembodiments, a halogenated biogenic activated carbon product adsorbs,absorbs and/or chemisorbs a selected contaminant in greater amounts thana comparable amount of a non-biogenic activated carbon product. In somesuch embodiments, the selected contaminant is a metal, a hazardous airpollutant, an organic compound (such as a VOC), a non-condensable gas,or any combination thereof. In some embodiments, the selectedcontaminant comprises mercury. In some embodiments, the selectedcontaminant comprises one or more VOCs. In some embodiments, thebiogenic activated carbon comprises at least about 1 wt % hydrogenand/or at least about 10 wt % oxygen.

Hazardous air pollutants are those pollutants that cause or may causecancer or other serious health effects, such as reproductive effects orbirth defects, or adverse environmental and ecological effects. Section112 of the Clean Air Act, as amended, is incorporated by referenceherein in its entirety. Pursuant to the Section 112 of the Clean AirAct, the United States Environmental Protection Agency (EPA) is mandatedto control 189 hazardous air pollutants. Any current or future compoundsclassified as hazardous air pollutants by the EPA are included inpossible selected contaminants in the present context.

Volatile organic compounds, some of which are also hazardous airpollutants, are organic chemicals that have a high vapor pressure atordinary, room-temperature conditions. Examples include short-chainalkanes, olefins, alcohols, ketones, and aldehydes. Many volatileorganic compounds are dangerous to human health or cause harm to theenvironment. EPA regulates volatile organic compounds in air, water, andland. EPA's definition of volatile organic compounds is described in 40CFR Section 51.100, which is incorporated by reference herein in itsentirety.

Non-condensable gases are gases that do not condense under ordinary,room-temperature conditions. Non-condensable gas may include, but arenot limited to, nitrogen oxides, carbon monoxide, carbon dioxide,hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane,ethylene, ozone, ammonia, or combinations thereof.

Multiple contaminants may be removed by the halogenated activated carbonparticles disclosed herein. In some embodiments, thecontaminant-adsorbed halogenated carbon particles include at least twocontaminants, at least three contaminants, or more. The halogenatedbiogenic activated carbon compositions disclosed herein can allowmulti-pollutant control as well as control of certain targetedpollutants (e.g. selenium).

In some embodiments, the contaminant-adsorbed halogenated activatedcarbon particles include at least one, at least two, at least three, orall of, carbon dioxide, nitrogen oxides, mercury, and sulfur dioxide (inany combination).

The separation in step (d) may include filtration (e.g., fabric filters)or electrostatic precipitation (ESP), for example. Fabric filters, alsoknown as baghouses, may utilize engineered fabric filter tubes,envelopes, or cartridges, for example. There are several types ofbaghouses, including pulse-jet, shaker-style, and reverse-air systems.The separation in step (d) may also include scrubbing.

An electrostatic precipitator, or electrostatic air cleaner, is aparticulate collection device that removes particles from a flowing gasusing the force of an induced electrostatic charge. Electrostaticprecipitators are highly efficient filtration devices that minimallyimpede the flow of gases through the device, and can easily remove fineparticulate matter from the air stream. An electrostatic precipitatorapplies energy only to the particulate matter being collected andtherefore is very efficient in its consumption of energy (electricity).

The electrostatic precipitator may be dry or wet. A wet electrostaticprecipitator operates with saturated gas streams to remove liquiddroplets such as sulfuric acid mist from industrial process gas streams.Wet electrostatic precipitators may be useful when the gases are high inmoisture content, contain combustible particulate, or have particlesthat are sticky in nature.

In some embodiments, the contaminant-adsorbed halogenated activatedcarbon particles are treated to regenerate the activated carbonparticles. In some embodiments, the method includes thermally oxidizingthe contaminant-adsorbed halogenated activated carbon particles. Thecontaminant-adsorbed halogenated activated carbon particles, or aregenerated form thereof, may be combusted to provide energy.

In some embodiments, the gas-phase emissions stream is derived fromcombustion of a fuel comprising the halogenated biogenic activatedcarbon composition.

In some embodiments relating specifically to mercury removal, a methodof using a halogenated biogenic activated carbon composition to reducemercury emissions comprises:

(a) providing halogenated activated carbon particles comprising abiogenic activated carbon composition that includes iron or aniron-containing compound;

(b) providing a gas-phase emissions stream comprising mercury;

(c) introducing the halogenated activated carbon particles into thegas-phase emissions stream, to adsorb at least a portion of the mercuryonto the activated carbon particles, thereby generating mercury-adsorbedcarbon particles within the gas-phase emissions stream; and

(d) separating at least a portion of the mercury-adsorbed halogenatedcarbon particles from the gas-phase emissions stream using electrostaticprecipitation or filtration, to produce a mercury-reduced gas-phaseemissions stream.

In some embodiments, a method of using a halogenated biogenic activatedcarbon composition to reduce emissions (e.g., mercury) further comprisesusing the halogenated biogenic activated carbon as a fuel source. Insuch embodiments, the high heat value of the halogenated biogenicactivated carbon product can be utilized in addition to its ability toreduce emissions by adsorbing, absorbing and/or chemisorbing potentialpollutants. Thus, in an example embodiment, the halogenated biogenicactivated carbon product, when used as a fuel source and as a mercurycontrol product, prevents at least 70% of mercury from emanating from apower plant, for example about 70%, about 75%, about 80%, about 85%,about 90%, about 95%, about 96%, about 97%, about 98%, 98.5%, about 99%,about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about99.6%, about 99.7%, about 99.8%, about 99.9%, or greater than about99.9% of mercury.

As an exemplary embodiment, halogenated biogenic activated carbon may beinjected (such as into the ductwork) upstream of a particulate mattercontrol device, such as an electrostatic precipitator or fabric filter.In some cases, a flue gas desulfurization (dry or wet) system may bedownstream of the halogenated activated carbon injection point. Thehalogenated activated carbon may be pneumatically injected as a powder.The injection location will typically be determined by the existingplant configuration (unless it is a new site) and whether additionaldownstream particulate matter control equipment is modified.

For boilers currently equipped with particulate matter control devices,implementing halogenated biogenic activated carbon injection for mercurycontrol could entail: (i) injection of powdered halogenated activatedcarbon upstream of the existing particulate matter control device(electrostatic precipitator or fabric filter); (ii) injection ofpowdered halogenated activated carbon downstream of an existingelectrostatic precipitator and upstream of a retrofit fabric filter; or(iii) injection of powdered halogenated activated carbon betweenelectrostatic precipitator electric fields.

In some embodiments, powdered halogenated biogenic activated carboninjection approaches may be employed in combination with existing SO₂control devices. Halogenated activated carbon could be injected prior tothe SO₂ control device or after the SO₂ control device, subject to theavailability of a means to collect the halogenated activated carbonsorbent downstream of the injection point.

When electrostatic precipitation is employed, the presence of iron or aniron-containing compound in the halogenated activated carbon particlescan improve the effectiveness of electrostatic precipitation, therebyfurther improving a process of controlling mercury emissions.

The method optionally further includes separating the mercury-adsorbedhalogenated carbon particles, containing the iron or an iron-containingcompound, from carbon or ash particles that do not contain the iron oran iron-containing compound. The carbon or ash particles that do notcontain the iron or an iron-containing compound may be recovered forrecycling, selling as a co-product, or other use. Any separationsinvolving iron or materials containing iron may employ magneticseparation, taking advantage of the magnetic properties of iron.

A halogenated biogenic activated carbon composition that includes ironor an iron-containing compound may be a “magnetic activated carbon”product. That is, the material is susceptible to a magnetic field. Theiron or iron-containing compound may be separated using magneticseparation devices. Additionally, the halogenated biogenic activatedcarbon, which includes iron, may be separated using magnetic separation.When magnetic separation is to be employed, magnetic metal separatorsmay be magnet cartridges, plate magnets, or another suitableconfiguration.

Inclusion of iron or iron-containing compounds may drastically improvethe performance of electrostatic precipitators for mercury control.Furthermore, inclusion of iron or iron-containing compounds maydrastically change end-of-life options, since the spent activated carbonsolids may be separated from other ash.

In some embodiments, a magnetic halogenated activated carbon product canbe separated out of the ash stream. Under the ASTM standards for use offly ash in cement, the fly ash must come from coal products. Ifwood-based activated carbon can be separated from other fly ash, theremainder of the ash may be used per the ASTM standards for cementproduction. Similarly, the ability to separate mercury-laden ash mayallow it to be better handled and disposed of, potentially reducingcosts of handling all ash from a certain facility.

In some embodiments, the same physical material may be used in multipleprocesses, either in an integrated way or in sequence. Thus, forexample, a halogenated activated carbon may, at the end of its usefullife as a performance material, then be introduced to a combustionprocess for energy value or to a metal process, etc.

For example, a halogenated activated carbon injected into an emissionsstream may be suitable to remove contaminants, followed by combustion ofthe activated carbon particles and possibly the contaminants, to produceenergy and thermally destroy or chemically oxidize the contaminants.

In some embodiments, the present disclosure provides a process forenergy production comprising:

(a) providing a carbon-containing feedstock comprising a halogenatedbiogenic activated carbon composition (which may optionally include oneor more additives); and

(b) oxidizing the carbon-containing feedstock to generate energy and agas-phase emissions stream,

wherein the presence of the halogenated biogenic activated carboncomposition within the carbon-containing feedstock is effective toadsorb at least one contaminant produced as a byproduct of the oxidizingor derived from the carbon-containing feedstock, thereby reducingemissions of the contaminant.

In some embodiments, the contaminant, or a precursor thereof, iscontained within the carbon-containing feedstock. In other embodiments,the contaminant is produced as a byproduct of the oxidizing.

The carbon-containing feedstock may further include biomass, coal, orany other carbonaceous material, in addition to the halogenated biogenicactivated carbon composition. In certain embodiments, thecarbon-containing feedstock consists essentially of the halogenatedbiogenic activated carbon composition as the sole fuel source.

The selected contaminant may be a metal selected from the groupconsisting of mercury, boron, selenium, arsenic, and any compound, salt,and mixture thereof; a hazardous air pollutant; an organic compound(such as a VOC); a non-condensable gas selected from the groupconsisting of nitrogen oxides, carbon monoxide, carbon dioxide, hydrogensulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene,ozone, and ammonia; or any combinations thereof. In some embodiments, ahalogenated biogenic activated carbon product adsorbs, absorbs and/orchemisorbs a selected contaminant in greater amounts than a comparableamount of a non-biogenic activated carbon product. In some suchembodiments, the selected contaminant is a metal, a hazardous airpollutant, an organic compound (such as a VOC), a non-condensable gas,or any combination thereof. In some embodiments, the selectedcontaminant comprises mercury. In some embodiments, the selectedcontaminant comprises one or more VOCs. In some embodiments, thehalogenated biogenic activated carbon comprises at least about 1 wt %hydrogen and/or at least about 10 wt % oxygen.

The halogenated biogenic activated carbon and the principles of thedisclosure may be applied to liquid-phase applications, includingprocessing of water, aqueous streams of varying purities, solvents,liquid fuels, polymers, molten salts, and molten metals, for example. Asintended herein, “liquid phase” includes slurries, suspensions,emulsions, multiphase systems, or any other material that has (or may beadjusted to have) at least some amount of a liquid state present.

In one embodiment, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to purify a liquid,the method comprising:

(a) providing halogenated activated carbon particles comprising abiogenic activated carbon composition;

(b) providing a liquid comprising at least one selected contaminant; and

(c) contacting the liquid with the halogenated activated carbonparticles to adsorb at least a portion of the at least one selectedcontaminant onto the activated carbon particles, thereby generatingcontaminant-adsorbed carbon particles and a contaminant-reduced liquid.

In some embodiments, the selected contaminant (in the liquid to betreated) is a metal, such as a metal selected from the group consistingof arsenic, boron, selenium, mercury, and any compound, salt, andmixture thereof. In some embodiments, the selected contaminant is anorganic compound (such as a VOC), a halogen, a biological compound, apesticide, or a herbicide. The contaminant-adsorbed halogenated carbonparticles may include two, three, or more contaminants. In someembodiments, a halogenated biogenic activated carbon product adsorbs,absorbs and/or chemisorbs a selected contaminant in greater amounts thana comparable amount of a non-biogenic activated carbon product. In somesuch embodiments, the selected contaminant is a metal, a hazardous airpollutant, an organic compound (such as a VOC), a non-condensable gas,or any combination thereof. In some embodiments, the selectedcontaminant comprises mercury. In some embodiments, the selectedcontaminant comprises one or more VOCs. In some embodiments, thehalogenated biogenic activated carbon comprises at least about 1 wt %hydrogen and/or at least about 10 wt % oxygen.

The liquid to be treated will typically be aqueous, although that is notnecessary for the principles of this disclosure. In some embodiments,step (c) includes contacting the liquid with the halogenated activatedcarbon particles in a fixed bed. In other embodiments, step (c) includescontacting the liquid with the halogenated activated carbon particles insolution or in a moving bed.

In one embodiment, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to remove at least aportion of a sulfur-containing contaminant from a liquid, the methodcomprising:

(a) providing halogenated activated-carbon particles comprising abiogenic activated carbon composition;

(b) providing a liquid containing a sulfur-containing contaminant; and

(c) contacting the liquid with the halogenated activated-carbonparticles to adsorb or absorb at least a portion of thesulfur-containing contaminant onto or into the halogenatedactivated-carbon particles.

In some embodiments, the sulfur-containing contaminant is selected fromthe group consisting of elemental sulfur, sulfuric acid, sulfurous acid,sulfur dioxide, sulfur trioxide, sulfate anions, bisulfate anions,sulfite anions, bisulfite anions, thiols, sulfides, disulfides,polysulfides, thioethers, thioesters, thioacetals, sulfoxides, sulfones,thiosulfinates, sulfimides, sulfoximides, sulfonediimines, sulfurhalides, thioketones, thioaldehydes, sulfur oxides, thiocarboxylicacids, thioamides, sulfonic acids, sulfinic acids, sulfenic acids,sulfonium, oxosulfonium, sulfuranes, persulfuranes, and combinations,salts, or derivatives thereof. For example, the sulfur-containingcontaminant may be a sulfate, in anionic and/or salt form.

In some embodiments, the halogenated biogenic activated carboncomposition comprises 55 wt % or more total carbon; a halogenatedcompound and a salt in a total amount of about 0.2 wt % to about 20 wt%; 15 wt % or less hydrogen; and 1 wt % or less nitrogen.

In some embodiments, step (c) includes filtration of the liquid. Inthese or other embodiments, step (c) includes osmosis of the liquid. Thehalogenated activated-carbon particles may be directly introduced to theliquid prior to osmosis. The halogenated activated-carbon particles maybe employed in pre-filtration prior to osmosis. In certain embodiments,the halogenated activated-carbon particles are incorporated into amembrane for osmosis. For example, known membrane materials such ascellulose acetate may be modified by introducing the halogenatedactivated-carbon particles within the membrane itself or as a layer onone or both sides of the membrane. Various thin-film carbon-containingcomposites could be fabricated with the halogenated activated-carbonparticles and additives.

In some embodiments, step (c) includes direct addition of thehalogenated activated-carbon particles to the liquid, followed by forexample sedimentation of the halogenated activated-carbon particles withthe sulfur-containing contaminant from the liquid.

The liquid may be an aqueous liquid, such as water. In some embodiments,the water is wastewater associated with a process selected from thegroup consisting of metal mining, acid mine drainage, mineralprocessing, municipal sewer treatment, pulp and paper, ethanol, and anyother industrial process that is capable of dischargingsulfur-containing contaminants in wastewater. The water may also be (orbe part of) a natural body of water, such as a lake, river, or stream.

In one embodiment, the present disclosure provides a process to reducethe concentration of sulfates in water, the process comprising:

(a) providing halogenated activated-carbon particles comprising abiogenic activated carbon composition;

(b) providing a volume or stream of water containing sulfates; and

(c) contacting the water with the activated-carbon particles and theadditive, to adsorb or absorb at least a portion of the sulfates onto orinto the activated-carbon particles.

In some embodiments, the sulfates are reduced to a concentration ofabout 50 mg/L or less in the water, such as a concentration of about 10mg/L or less in the water. In some embodiments, the sulfates arereduced, as a result of absorption and/or adsorption into the biogenicactivated carbon composition, to a concentration of about 100 mg/L, 75mg/L, 50 mg/L, 25 mg/L, 20 mg/L, 15 mg/L, 12 mg/L, 10 mg/L, 8 mg/L, orless in the wastewater stream. In some embodiments, the sulfate ispresent primarily in the form of sulfate anions and/or bisulfate anions.Depending on pH, the sulfate may also be present in the form of sulfatesalts.

The water may be derived from, part of, or the entirety of a wastewaterstream. Exemplary wastewater streams are those that may be associatedwith a metal mining, acid mine drainage, mineral processing, municipalsewer treatment, pulp and paper, ethanol, or any other industrialprocess that could discharge sulfur-containing contaminants towastewater. The water may be a natural body of water, such as a lake,river, or stream. In some embodiments, the process is conductedcontinuously. In other embodiments, the process is conducted in batch.

The halogenated biogenic activated carbon composition comprises 55 wt %or more total carbon; a halogenated compound and a salt in a totalamount of about 0.2 wt % to about 20 wt %; 15 wt % or less hydrogen; and1 wt % or less nitrogen, in some embodiments.

Step (c) may include, but is not limited to, filtration of the water,osmosis of the water, and/or direct addition (with sedimentation,clarification, etc.) of the activated-carbon particles to the water.

When osmosis is employed, the halogenated activated carbon can be usedin several ways within, or to assist, an osmosis device. In someembodiments, the halogenated activated-carbon particles are directlyintroduced to the water prior to osmosis. The halogenatedactivated-carbon particles are optionally employed in pre-filtrationprior to the osmosis. In certain embodiments, the halogenatedactivated-carbon particles are incorporated into a membrane for osmosis.

The present disclosure also provides a method of using a halogenatedbiogenic activated carbon composition to remove a sulfur-containingcontaminant from a gas phase, the method comprising:

(a) providing halogenated activated-carbon particles comprising abiogenic activated carbon composition;

(b) providing a gas-phase emissions stream comprising at least onesulfur-containing contaminant;

(c) introducing the activated-carbon particles and the additive into thegas-phase emissions stream, to adsorb or absorb at least a portion ofthe sulfur-containing contaminant onto the activated-carbon particles;and

(d) separating at least a portion of the activated-carbon particles fromthe gas-phase emissions stream.

In some embodiments, the sulfur-containing contaminant is selected fromthe group consisting of elemental sulfur, sulfuric acid, sulfurous acid,sulfur dioxide, sulfur trioxide, sulfate anions, bisulfate anions,sulfite anions, bisulfite anions, thiols, sulfides, disulfides,polysulfides, thioethers, thioesters, thioacetals, sulfoxides, sulfones,thiosulfinates, sulfimides, sulfoximides, sulfonediimines, sulfurhalides, thioketones, thioaldehydes, sulfur oxides, thiocarboxylicacids, thioamides, sulfonic acids, sulfinic acids, sulfenic acids,sulfonium, oxosulfonium, sulfuranes, persulfuranes, and combinations,salts, or derivatives thereof.

The halogenated biogenic activated carbon composition may include 55 wt% or more total carbon; a halogenated compound and a salt in a totalamount of about 0.2 wt % to about 20 wt %; 15 wt % or less hydrogen; 1wt % or less nitrogen; and an optional additive selected from an acid, abase, a salt, a metal, a metal oxide, a metal hydroxide, or acombination thereof. The optional additive may be provided as part ofthe activated-carbon particles, or may be introduced directly into thegas-phase emissions stream.

In some embodiments, the gas-phase emissions stream is derived fromcombustion of a fuel comprising the halogenated biogenic activatedcarbon composition. For example, the gas-phase emissions stream may bederived from co-combustion of coal and the halogenated biogenicactivated carbon composition.

In some embodiments, separating in step (d) comprises filtration. Inthese or other embodiments, separating in step (d) compriseselectrostatic precipitation. In any of these embodiments, separating instep (d) may include scrubbing, which may be wet scrubbing, dryscrubbing, or another type of scrubbing.

The halogenated biogenic activated carbon composition may furthercomprise 0.5 wt % or less phosphorus; and 0.2 wt % or less sulfur.

The contaminant-adsorbed halogenated activated carbon particles may befurther treated to regenerate the halogenated activated carbonparticles. After regeneration, the halogenated activated carbonparticles may be reused for contaminant removal, or may be used foranother purpose, such as combustion to produce energy. In someembodiments, the contaminant-adsorbed halogenated activated carbonparticles are directly oxidized (without regeneration) to produceenergy. In some embodiments, the oxidation occurs in the presence of anemissions control device (e.g., a second amount of fresh or regeneratedactivated carbon particles) to capture contaminants released from theoxidation of the contaminant-absorbed halogenated activated carbonparticles.

In some embodiments, halogenated biogenic activated carbon according tothe present disclosure can be used in any other application in whichtraditional activated carbon (e.g., halogenated activated carbon) mightbe used. In some embodiments, the halogenated biogenic activated carbonis used as a total (i.e., 100%) replacement for traditional halogenatedactivated carbon. In some embodiments, halogenated biogenic activatedcarbon comprises essentially all or substantially all of the activatedcarbon used for a particular application. In some embodiments, ahalogenated activated carbon composition comprises about 1% to about100% of halogenated biogenic activated carbon, for example, about 1%,about 2%, about 5%, about 10%, about 15%, about 20%, about 25%, about30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%,about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about95%, about 96%, about 97%, about 98%, about 99%, or about 100%halogenated biogenic activated carbon.

For example and without limitation, halogenated biogenic activatedcarbon can be used—alone or in combination with a traditionalhalogenated activated carbon product—in filters. In some embodiments, afilter comprises an halogenated activated carbon component consistingof, consisting essentially of, or consisting of a halogenated biogenicactivated carbon. In some embodiments, a filter comprises a halogenatedactivated carbon component comprising about 1% to about 100% ofhalogenated biogenic activated carbon, for example, about 1%, about 2%,about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%,about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about96%, about 97%, about 98%, about 99%, or about 100% halogenated biogenicactivated carbon.

In some embodiments, a packed bed or packed column comprises ahalogenated activated carbon component consisting of, consistingessentially of, or consisting of a halogenated biogenic activatedcarbon. In some embodiments, a packed bed or packed column comprises ahalogenated activated carbon component comprising about 1% to about 100%of halogenated biogenic activated carbon, for example, about 1%, about2%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%,about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%,about 96%, about 97%, about 98%, about 99%, or about 100% halogenatedbiogenic activated carbon. In such embodiments, the halogenated biogenicactivated carbon has a size characteristic suitable for the particularpacked bed or packed column.

The above description should not be construed as limiting in any way asto the potential applications of the halogenated biogenic activatedcarbon. Injection of halogenated biogenic activated carbon into gasstreams may be useful for control of contaminant emissions in gasstreams or liquid streams derived from coal-fired power plants,biomass-fired power plants, metal processing plants, crude-oilrefineries, chemical plants, polymer plants, pulp and paper plants,cement plants, waste incinerators, food processing plants, gasificationplants, and syngas plants.

Essentially any industrial process or site that employs fossil fuel orbiomass for generation of energy or heat, can benefit from gas treatmentby the halogenated biogenic activated carbon provided herein. Forliquid-phase applications, a wide variety of industrial processes thatuse or produce liquid streams can benefit from treatment by thehalogenated biogenic activated carbon provided herein.

Additionally, when the halogenated biogenic activated carbon isco-utilized as a fuel source, either in parallel with its use forcontaminant removal or in series following contaminant removal (andoptionally following some regeneration), the halogenated biogenicactivated carbon (i) has lower emissions per Btu energy output thanfossil fuels; (ii) has lower emissions per Btu energy output thanbiomass fuels; and (iii) can reduce emissions from biomass or fossilfuels when co-fired with such fuels. It is noted that the halogenatedbiogenic activated carbon may also be mixed with coal or other fossilfuels and, through co-combustion, the halogenated biogenic activatedcarbon enables reduced emissions of mercury, SO₂, or other contaminants.

In one embodiment, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to remove at least aportion of odor-producing or taste-producing compounds, such as, but notlimited to, MIB or Geosmin, from a liquid.

In one embodiment, the present disclosure provides a method of using ahalogenated biogenic activated carbon composition to remove color from amaterial or compound, such as in sugar production.

EXAMPLES

Test Bed Preparation

As depicted in FIG. 1, a tension ring was placed into a glass tube(e.g., having an internal diameter of about ½-inch and a length of about4 inches) and pushed three-fourths of the way down. A glass fiber filterwas placed onto the tension ring. A second tension ring was then placedon top of the glass fiber filter to keep the glass fiber filter frommoving. Approximately 16.3 milligrams of a halogenated activated carboncomposition was placed on the glass fiber filter. A third tension ringwas placed into the glass tube one-fourth of the way down. Three glassfiber filters were then placed on top of the ring, followed by anothertension ring. The glass tube was labeled with the sample I.D. and placedinto the adsorption analysis setup described in more detail below.

Test Bed Analysis

For mercury adsorption analysis, an analysis system consistent with FIG.2 (e.g., an Ohio Lumex mercury analyzer such as model RA915+ and RP-M324M) was used. Mercury vapor was generated from a mercury perm tubethat was placed inside a quartz glass tube. The quartz tube was locatedin a Lindberg tube furnace which was heated to 125° C. A diaphragm pumpwas used to pull the mercury vapor-laden air through the test bed andanalyzer at a rate of 2 L/min.

Preparation of Samples

Various samples of halogenated activated carbon compositions consistentwith the present disclosure were generated for testing. First, a 12.5%solution in water was made for each halogen compound or mixture to betested. An amount of the 12.5% solution was sprayed onto one gram ofpowdered activated carbon to produce the halogenated activated carboncompositions having a desired weight-percent of the halogen species. Thehalogenated activated carbon compositions were allowed to air-dryovernight to produce halogenated activated carbon compositionscomprising 6 wt % of the halogen compound or salt (e.g., 6 wt % totalhalide content).

Total halide content of salt mixtures (e.g., Dead Sea Salt) wasdetermined according to Formula (1):

q ₁ +q ₂ +q ₃ + . . . q _(n),  (1)

wherein q_(A) is the amount of halogenated salt X in the salt mixture,and wherein each q_(x) is determined according to Formula (2):

q _(A)=(Q _(A))(MW _(X))/(MW _(A)),  (2)

wherein Q_(A) is the weight in grams of halogenated compound A in thesalt mixture (e.g., as determined experimentally and/or as indicated ona certificate of analysis), MW_(X) is the total molecular weight ofhalogen X in the halogenated compound (e.g., accounting for theempirical formula of halogenated compound A), and MW_(A) is themolecular weight of halogenated compound A.

The amount of a salt mixture (e.g., Dead Sea Salt) required to produce aY % aqueous solution may be determined according to Formula (3):

Amount=(Y/100)(VOL_(mL))/(q ₁ +q ₂ +q ₃ + . . . q _(n))/100,  (3)

wherein Amount is the amount in grams of the salt mixture required,VOL_(mL) is the volume of water in milliliters, and (q₁+q₂+q₃+ . . .q_(n)) is the total amount of halogen in the salt mixture, for exampleas determined by Formulas (1) and/or (2).

For example, each gram of a Dead Sea Salt composition comprising 32.67%magnesium chloride (MgCl₂), 23.09% potassium chloride (KCl) and 4.58%sodium chloride (NaCl) would include 326.7 mg of MgCl₂, 230.9 mg of KCl,and 45.8 mg of NaCl, corresponding to a total halogen amount of 380.9 mg(243.3 mg from MgCl₂, 109.8 mg from KCl, and 27.8 mg from NaCl).

Preparation of 10 mL of a 12.5% aqueous solution would thus require 3.28g of the Dead Sea Salt composition described above. That 10 mL solutionwould include 1.25 g of total halogen (3.28 g of Dead Sea Salt×0.3809 gtotal halogen/g of Dead Sea Salt) and would be sufficient to prepare20.8 g of halogenated activated carbon having a total halogen content ofabout 6 wt % (e.g., 0.48 mL per gram of activated carbon).

Analysis of Samples

FIG. 3 shows a graph of experimental results on mercury adsorption overtime based on this procedure, using various halogenated compounds/saltsin activated carbon at 6 wt % total halide. Two samples of Norit BCactivated carbon were also tested as comparative controls. Lower valueson the y-axis correspond to lower mercury breakthrough, i.e. highermercury adsorption into the sample. As shown in FIG. 3, the copperhalide salts and the Dead Sea salt outperform most of the othermaterials. These data highlight the complex and unpredictable nature ofthe presence of additional chemical species in activated carboncompositions.

In this detailed description, reference has been made to multipleembodiments of the disclosure and non-limiting examples relating to howthe disclosure can be understood and practiced. Other embodiments thatdo not provide all of the features and advantages set forth herein maybe utilized, without departing from the spirit and scope of the presentdisclosure. This disclosure incorporates routine experimentation andoptimization of the methods and systems described herein. Suchmodifications and embodiments are considered to be within the scope ofthe disclosure defined by the claims.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps may be modified and thatsuch modifications are in accordance with the embodiments of thedisclosure. Additionally, certain of the steps may be performedconcurrently in a parallel process when possible, as well as performedsequentially.

Therefore, to the extent there are embodiments of the disclosure whichare within the spirit of the disclosure or equivalent to the inventionsfound in the appended claims, it is the intent that this patent willcover those embodiments as well. The present invention shall only belimited by what is claimed.

What is claimed is:
 1. A halogenated activated carbon composition, thecomposition comprising, on a dry basis: at least about 85 wt % carbon; ahalogenated compound; and a salt; wherein the halogenated compound andthe salt are present in a total amount of at least about 0.1 wt % to atmost about 15 wt %.
 2. The halogenated activated carbon composition ofclaim 1, wherein the composition comprises at least about 90 wt %carbon.
 3. The halogenated activated carbon composition of claim 2,wherein the composition comprises at least about 95 wt % carbon.
 4. Thehalogenated activated carbon composition of claim 1, wherein the carbonis biogenic carbon.
 5. The halogenated activated carbon composition ofclaim 1, wherein the halogenated compound and the salt are present in atotal amount of at least about 1 wt % to at most about 10 wt %.
 6. Thehalogenated activated carbon composition of claim 1, wherein thehalogenated compound comprises at least one of magnesium chloride,potassium chloride, sodium chloride, and calcium chloride; and whereinthe salt comprises at least one of magnesium chloride, potassiumchloride, sodium chloride, and calcium chloride that is different thanthe halogenated compound.
 7. The halogenated activated carboncomposition of claim 1, wherein the halogenated compound or the saltcomprises at least one anion selected from the group consisting ofchloride, bromide, iodide, fluoride, sulfate, nitrate, and phosphate. 8.The halogenated activated carbon composition of claim 7, wherein thehalogenated compound or the salt comprises at least two anions selectedfrom the group consisting of chloride, bromide, iodide, fluoride,sulfate, nitrate, and phosphate.
 9. The halogenated activated carboncomposition of claim 1, wherein the halogenated compound or the saltcomprises at least one cation selected from the group consisting ofmagnesium, potassium, calcium, sodium, ammonium, copper, cobalt, nickel,manganese, iron, zinc, molybdenum, and tungsten.
 10. The halogenatedactivated carbon composition of claim 9, wherein the halogenatedcompound or the salt comprises at least two cations selected from thegroup consisting of magnesium, potassium, calcium, sodium, ammonium,copper, cobalt, nickel, manganese, iron, zinc, molybdenum, and tungsten.11. The halogenated activated carbon composition of claim 1, wherein thehalogenated compound or the salt is derived from a naturally occurringsalt mixture.
 12. The halogenated activated carbon composition of claim1, wherein the halogenated compound or the salt is a naturally occurringsalt mixture, and wherein the naturally occurring salt mixture is from asource selected from the group consisting of ocean water, salt lakewater, rock salt, salt brine wells, and combinations thereof.
 13. Thehalogenated activated carbon composition of claim 11, wherein thenaturally occurring salt mixture comprises, consists essentially of, orconsists of Dead Sea salt.
 14. The halogenated activated carboncomposition of claim 11, wherein the naturally occurring salt mixturecomprises, consists essentially of, or consists of Dead Sea salt andGreat Salt Lake salt.
 15. The halogenated activated carbon compositionof claim 11, wherein the naturally occurring salt mixture comprises,consists essentially of, or consists of Dead Sea salt and sea saltderived from ocean water.
 16. The halogenated activated carboncomposition of claim 1, wherein the halogenated compound or the saltcomprises at least about 10 wt % to at most about 90 wt % magnesiumchloride.
 17. The halogenated activated carbon composition of claim 16,wherein the halogenated compound or the salt comprises at least about 25wt % to at most about 40 wt % magnesium chloride.
 18. The halogenatedactivated carbon composition of claim 1, wherein the halogenatedcompound or the salt comprises at least about 5 wt % to at most about 75wt % potassium chloride.
 19. The halogenated activated carboncomposition of claim 18, wherein the halogenated compound or the saltcomprises at least about 15 wt % to at most about 35 wt % potassiumchloride.
 20. The halogenated activated carbon composition of claim 1,wherein the halogenated compound or the salt comprises at least about 1wt % to at most about 25 wt % sodium chloride.
 21. The halogenatedactivated carbon composition of claim 20, wherein the halogenatedcompound or the salt comprises at least about 2 wt % to at most about 10wt % sodium chloride.
 22. The halogenated activated carbon compositionof claim 1, wherein the halogenated compound or the salt comprisesmagnesium chloride (MgCl₂), potassium chloride (KCl), and sodiumchloride (NaCl); and wherein the weight ratio of (MgCl₂+KCl)/NaCl is atleast about
 5. 23. The halogenated activated carbon composition of claim22, wherein the weight ratio of (MgCl₂+KCl)/NaCl is at least about 10.24. The halogenated activated carbon composition of claim 1, wherein thehalogenated compound or the salt comprises at least about 0.1 wt % to atmost about 5 wt % bromide ions.
 25. The halogenated activated carboncomposition of claim 24, wherein the halogenated compound or the saltcomprises at least about 0.2 wt % to at most about 2 wt % bromide ions.26. The halogenated activated carbon composition of claim 1, wherein thehalogenated compound or the salt comprises at least about 0.01 wt % toat most about 1 wt % sulfate ions.
 27. The halogenated activated carboncomposition of claim 26, wherein the halogenated compound or the saltcomprises at least about 0.01 wt % to at most about 0.5 wt % sulfateions.
 28. A biogenic activated carbon composition comprising, on a drybasis: at least 80 wt % total carbon; at most 10 wt % hydrogen; and afirst salt comprising a halogenated compound selected from the groupconsisting of magnesium chloride, potassium chloride, sodium chloride,calcium chloride, and combinations thereof; and a second salt; whereinthe halogenated compound and the second salt are present in a totalamount of at least about 0.2 wt % to at most about 20 wt %, and whereinthe second salt is optionally halogenated.
 29. The biogenic activatedcarbon composition of claim 28, wherein the first salt and the secondsalt are present in a total amount of at least about 1 wt % to at mostabout 15 wt %.
 30. The biogenic activated carbon composition of claim28, wherein the halogenated compound comprises at least about 10 wt % toat most about 90 wt % magnesium chloride.
 31. The biogenic activatedcarbon composition of claim 28, wherein the halogenated compoundcomprises at least about 5 wt % to at most about 75 wt % potassiumchloride.
 32. The biogenic activated carbon composition of claim 28,wherein the halogenated compound comprises at least about 1 wt % to atmost about 25 wt % sodium chloride.
 33. The biogenic activated carboncomposition of claim 28, wherein the halogenated compound containsmagnesium chloride (MgCl₂), potassium chloride (KCl), and sodiumchloride (NaCl), and wherein the weight ratio of (MgCl₂+KCl)/NaCl is atleast about
 5. 34. The biogenic activated carbon composition of claim28, wherein the halogenated compound comprises at least about 0.1 wt %to at most about 5 wt % bromide ions.
 35. The biogenic activated carboncomposition of claim 28, wherein the halogenated compound comprises atleast about 0.01 wt % to at most about 1 wt % sulfate ions.
 36. Thebiogenic activated carbon composition of claim 28, wherein the firstsalt or the second salt are a naturally occurring salt mixture.
 37. Thebiogenic activated carbon composition of claim 36, wherein the naturallyoccurring salt mixture is from a source selected from the groupconsisting of ocean water, salt lake water, rock salt, salt brine wells,and combinations thereof.